Curable coating compositions of silane functional polymers

ABSTRACT

There is a tin-free curable composition having (A) one or more organic polymers having a reactive-silicon-containing group, wherein at least one polymer has a main chain skeleton selected from the group consisting of polyoxyalkylene polymers, saturated hydrocarbon polymers, and (meth)acrylic acid ester polymers; (B) from 0.001 to 20 parts by weight for 100 parts by weight of the organic polymer(s) (A) of a silanol condensation catalyst consisting of one or more metal amidine complexes and one or more amine carboxylate salts, (C) a crosslinker or chain extender chosen from an alkoxysilane, an alkoxysiloxane, an oximosilane, an oximosiloxane, an epoxysilane, an epoxysiloxane, an aminosilane, a carboxysilane, a carboxysiloxane, an alkylamidosilane, an alkylamidosiloxane, an arylamidosilane, an arylamidosiloxane, an alkoxyaminosilane, an alkaryaminosiloxane, an alkoxycarbamatosilane, an alkoxycarbamatosiloxane, and combinations of two or more thereof; and (D) at least one adhesion promoter chosen from a silane or siloxane other than the compounds listed under (C). There is also a cured polymer formed from the tin-free curable composition.

CROSS-REFERENCE TO A RELATED APPLICATION

This application is a divisional of U.S. Ser. No. 15/049,846, filed Feb.22, 2016, now issued as U.S. Pat. No. 9,976,028, which claims priorityto U.S. Provisional Application Ser. No. 62/119,693, filed Feb. 23,2015, both of which are incorporated herein in its entirety.

BACKGROUND 1. Field of the Disclosure

The present disclosure relates to a curable composition comprising oneor more polymers having a silicon-containing group which has a hydroxylgroup or hydrolyzable group bonded to a silicon atom and can form asiloxane bond to be crosslinked (said silicon-containing group may bereferred to as a “reactive-silicon-containing group” hereinafter).

2. Description of the Related Art

It has been known that organic polymers, with at least one reactivesilicon group can polymerize with the formation of siloxane bond byhydrolysis and/or condensation reactions aided by moisture and suitablecatalysts even at room temperature, whereby the polymers are crosslinkedto give a fully cured product.

Among these polymers having a reactive silicon group, polymers whereinthe main chain skeleton thereof is a polyoxyalkylene polymer orpolyisobutylene polymer are well known and these polymers are alreadyproduced industrially, and are widely used in sealants, adhesives andpaints. The curable composition used in sealants, adhesives, or thelike, are required to have various desirable attributes such ascurability, adhesiveness, and mechanical property.

Polymers having reactive terminal silyl groups or compositionscomprising such polymers can be hydrolyzed and condensed in the presenceof water and organometallic catalysts. Suitable known catalysts forcurable compositions include organometallic compounds employing metalssuch as Sn, and Ti. Organotin compounds such as, for example, dibutyltindilaurate (DBTDL), and dibutyltin bis(acetylacetonate) are widely usedas condensation cure catalysts to accelerate the moisture assistedcuring of a number of different polyorganosiloxanes and non-siliconepolymers having reactive terminal silyl groups such as room temperaturevulcanizing (RTV) formulations including RTV-1 and RTV-2 formulations.Environmental regulatory agencies and directives, however, haveincreased or are expected to increase restrictions on the use oforganotin compounds in formulated products. For example, whileformulations with greater than 0.5 wt. % dibutyltin presently requirelabeling as toxic with reproductive 1B classification,dibutyltin-containing formulations are proposed to be completely phasedout in consumer applications during next several years.

Alternative organotin compounds such as dioctyltin compounds anddimethyltin compounds are only short-term remedies, as these organotincompounds may also be regulated in the future. It would be beneficial toidentify non-tin metal catalysts that accelerate the condensation curingof moisture curable silicones and non-silicones. Desirably, substitutesfor organotin catalysts should exhibit properties similar to organotincompounds in terms of curing, storage, and appearance. Non-tin catalystsshould also initiate the condensation reaction of the selected polymersand complete this reaction at the surface and in the bulk within adesired time frame.

The use of zinc complexes as catalysts in condensation curable siliconecompositions has been described. For example, U.S. Patent PublicationNos. 2011/0046304 and 2009/0156737; WO 2010/146253; and EP 1178150describe the use of zinc compounds for silyl condensation curechemistry.

U.S. Pat. No. 5,985,991 broadly claims the use of various metals in ageneric list of metal acetylacetonates consisting of Cu, Cr, Al, Zn, Ti,and Zr to improve the oil resistance of RTV silicone composition whichcomprises metal salt of carboxylic acid as a condensation cure catalyst.

U.S. Pat. No. 5,945,466 broadly claims a generic list of organic metalcompounds containing Sn, Ti, Zr, Pd, Zn, Co, Mn and Al as metallicelement, as curing catalyst for room temperature curableorganopolysiloxane composition which contains organosilane or itshydrolyzed product among other components.

U.S. Pat. No. 7,365,145 generically claims, a generic list of organicdibutyltin, zirconium complex, aluminum chelate, titanium chelate,organic zinc, organic cobalt, and organic nickel as catalysts inmoisture curable silylated polymer composition.

U.S. Publication No. 2009/0156737 claims a generic list of Lewis acidcompounds of Ti, Zr, Hf, Zn, B, Al as catalysts in polymer blendscomprising alkoxy silane terminated polymers and fillers.

U.S. Pat. No. 4,293,597 includes a generic list of metal salts includingPb, Sn, Zr, Sb, Cd, Ba, Ca, and Ti as catalysts in curable siliconerubber compositions that also contains nitrogen-functional silanes.

U.S. Pat. No. 4,461,867 includes a generic list of metal esters alsoincluding Sn, Pb, Zr, Sb, Cd, Ba, Ca, Ti, Mn, Zn, Cr, Co, Ni, Al, Ga andGe as a catalyst in moisture curable RTV-1 silicone compositions.

U.S. Patent Publication No. 2011/0098420 includes a generic listincluding compounds of Pt, Pd, Pb, Sn, Zn, Ti and Zr, as dehydrogenativecondensation reaction catalyst for a curable polysiloxane compositioncomprising of siloxanes with 2 or more hydrosilyl groups and siloxaneswith 2 or more silanol groups.

U.S. Pat. No. 7,527,838 claims a generic list of materials whichincludes metal catalysts based on Sn, Ti, Zr, Pb, Co, Sb, Mn and Zn, incurable diorganopolysiloxane compositions used for making insulatedglass units.

Despite these general teachings, there has not been provided anyteachings or catalyst compositions that improve on the catalyticactivity exhibited by synergistic mixtures of different metal amidinecomplexes and carboxylate salts of various amines. Further, there hasnot been a replacement catalyst for organo-tin compounds that maintainsits ability to cure after storage over months in a sealed cartridge,when exposed to humidity or ambient air. It is always a specificrequirement for moisture curable compositions to achieve the shortestpossible curing times, showing a tack-free surface as well as a curingthrough the complete bulk in thick section for “One-Part” and “Two-Part”Room-Temperature Vulcanizing (RTV) compositions and provide a reasonableadhesion after cure onto a variety of substrates.

JP-A-5-117519 discloses that the curing performance is abruptly improvedby using a carboxylic acid and an amine together, but these compositionssuffer from lack of sufficient adhesiveness. In addition, storagestability of such catalysts is undesirable and premature gelation canoccur during storage of such compositions.

SUMMARY OF THE DISCLOSURE

Described herein is a catalyst composition comprising a combination ofone or more metal amidine complexes with one or more amine carboxylatesalts, said composition being effective as a catalyst for reactions ofone or more organic polymers having a reactive-silicon-containing group,and a tin free polymer composition comprising said catalyst compositionand one or more organic polymers having a reactive-silicon-containinggroup. The tin free polymer composition of the disclosure exhibits goodcure, adhesiveness and storage stability.

Further according to the present invention, there are provided tin-free,curable compositions having silyl-terminated polymers and a non-toxiccondensation catalyst based on metal amidine complexes in combinationwith carboxylate salts of various amines.

In one embodiment, the metal amidine complexes described herein have ametal, an amidine, and a carboxylate. In certain embodiments, the metalamidine carboxylate complexes are metal (II) amidine carboxylatecomplexes. In a particular embodiment, the metal amidine complex is ofthe chemical formula M (amidine)_(w)(carboxylate)₂, where w is aninteger from 1 to 4, for example 2 or 4. In certain embodiments, themetal is zinc, lithium, sodium, magnesium, barium, potassium, calcium,bismuth, cadmium, aluminum, zirconium, hafnium, titanium, lanthanum,vanadium, niobium, tantalum, tellurium, molybdenum, tungsten, or cesium.In a particular embodiment, the metal is zinc. In a particularembodiment, the metal is in the +2 oxidation state.

In certain embodiments, the amidine of the metal amidine complex is anamidine of formulae I-VIII. In some particular embodiments the amidineis of formula (I)-(III), in some particular embodiments the amidine isof formula (IV)-(VIII), and in some particular embodiments amidines offormula (I)-(III) are excluded.

wherein R¹ is hydrogen, an organic group attached through a carbon atom,for example, C₁-C₃₆ alkyl, C₂-C₂₅ alkyl interrupted by oxygen or sulfur,C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which is unsubstituted or substitutedby C₁-C₄ allyl and/or carboxyl; C₅-C₁₅ cycloalkenyl which isunsubstituted or substituted by C₁-C₄ alkyl and/or carboxyl, C₁₃-C₂₆polycycloalkyl, C₇-C₉ phenylalkyl which is unsubstituted or substitutedon the phenyl ring by C₁-C₄ alkyl; an amine group which is optionallysubstituted; or a hydroxyl group which is optionally etherified with ahydrocarbyl group having up to 8 carbon atoms;R² and R³ are each independently hydrogen or an organic group attachedthrough a carbon atom, for example, C₁-C₂₅ alkyl, C₂-C₂₅ alkylinterrupted by oxygen or sulfur, C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl whichis unsubstituted or substituted by C₁-C₄ allyl and/or carboxyl, C₅-C₁₅cycloalkenyl which is unsubstituted or substituted by C₁-C₄ alkyl and/orcarboxyl, C₁₃-C₂₆ polycycloalkyl, C₇-C₉ phenylalkyl which isunsubstituted or substituted on the phenyl ring by C₁-C₄ alkyl, or R²and R³ are joined to one another by an N═C—N linkage to form aheterocyclic ring with one or more hetero atoms or a fused bicyclic ringwith one or more heteroatoms; R⁴ is hydrogen, an organic group attachedthrough a carbon atom (such as C₁-C₃₆ alkyl, C₁-C₃₆ alkyl interrupted byoxygen or sulfur; C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which isunsubstituted or substituted by C₁-C₄ allyl and/or carboxyl; C₅-C₁₅cycloalkenyl which is unsubstituted or substituted by C₁-C₄ alkyl and/orcarboxyl; C₁₃-C₂₆ polycycloalkyl, C₇-C₉ phenylalkyl which isunsubstituted or substituted on the phenyl ring by C₁-C₄ alkyl) or ahydroxyl group which can be optionally etherified with a hydrocarbylgroup having up to 8 carbon atoms; R⁵, R⁶, R⁷, and R⁸ are independentlyhydrogen, alkyl, substituted alkyl, hydroxyalkyl, aryl, aralkyl,cycloalkyl, heterocyclics, ether, thioether, halogen, —N(R)₂,polyethylene polyamines, nitro groups, keto groups, ester groups, orcarbonamide groups optionally alkyl substituted with alkyl, substitutedalkyl, hydroxyalkyl, aryl, aralkyl, cycloalkyl, heterocycles, ether,thioether, halogen, —N(R)₂, polyethylene polyamines, nitro groups, ketogroups or ester groups;R⁹, R¹⁰ and R¹¹ are independently hydrogen, alkyl, alkenyl or alkoxy of1 to 36 carbons, cycloalkyl of 6 to 32 carbons, alkylamino of 1 to 36carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl, hydroxyalkyl,hydroxycycloalkyl of 1 to 20 carbon atoms, methoxyalkyl of 1 to 20carbon atoms, aralkyl of 7 to 9 carbon atoms wherein the aryl group ofthe aralkyl is optionally substituted by alkyl of 1 to 36 carbon atoms,ether, thioether, halogen, —N(R″)₂, polyethylene polyamines, nitrogroups, keto groups, ester groups, or carbonamide groups and the alkylgroup of the aralkyl is optionally substituted with alkyl, substitutedalkyl, hydroxyalkyl, aryl, aralkyl, cycloalkyl, heterocyclics, ether,thioether, halogen, —N(R″)₂, polyethylene polyamines, nitro groups, ketogroups or ester groups, wherein R″ of —N(R″)₂ is alkyl, alkylene, aryl,aralkyl, cycloalkyl or heterocyclic radical, optionally substituted withhalogen, nitro, alkyl, alkoxy or amino, and, m=1 or 2 wherein when m=1,R is hydrogen or a plurality of radicals optionally joined by heteroatoms O, N or S; n=2 or 3;

wherein each of R₂₁, R₂₂, R₂₃, R₂₄, and R₂₅ is hydrogen, (cyclo)alkyl,aryl, aromatic, organometallic, a polymeric structure, or together canform a cycloalkyl, aryl, or an aromatic structure, and wherein R₂₁, R₂₂,R₂₃, R₂₄, and R₂₅ can be the same or different. As used herein,“(cyclo)alkyl” refers to both alkyl and cycloalkyl. When any of the Rgroups “together can form a (cyclo)alkyl, aryl, and/or aromatic group”it is meant that any two adjacent R groups may be connected to form acyclic moiety, such as the rings in structures (V)-(VIII) below.

It will be appreciated that in some embodiments, the double bond betweenthe carbon atom and the nitrogen atom that is depicted in structure (IV)may be located between the carbon atom and another nitrogen atom ofstructure (IV). Accordingly, the various substituents of structure (IV)may be attached to different nitrogens depending on where the doublebond is located within the structure.

In certain embodiments, the amidine comprises a cyclic guanidine ofstructure (IV) wherein two or more R groups of structure (IV) togetherform one or more rings. In other words, in some embodiments the cyclicguanidine comprises ≥1 ring. For example, the cyclic guanidine caneither be a monocyclic guanidine (1 ring) as depicted in structures (V)and/or (VI) below, or the cyclic guanidine can be polycyclic (≥2 rings)as depicted in structures (VII) and (VIII) above.

Each substituent of structures (V) and/or (VI), R₂₁-R₂₇, can comprisehydrogen, (cyclo)alkyl, aryl, aromatic, organometallic, a polymericstructure, or together can form a cycloalkyl, aryl, or an aromaticstructure, and wherein R₂₁-R₂₇ can be the same or different. Similarly,each substituent of structures (VII) and (VIII), R₂₁-R₂₉, can behydrogen, alkyl, aryl, aromatic, organometallic, a polymeric structure,or together can form a cycloalkyl, aryl, or an aromatic structure, andwherein R21-R29 can be the same or different. Moreover, in someembodiments of structures (V) and/or (VI), certain combinations ofR₂₁-R₂₇ may be part of the same ring structure. For example, R₂₁ and R₂₇of structure (V) may form part of a single ring structure. Moreover, insome embodiments, it will be understood that any combination ofsubstituents (R₂₁-R₂₇ of structures (V) and/or (VI) as well as R₂₁-R₂₉of structures (VII) and/or (VIII) can be chosen so long as thesubstituents do not substantially interfere with the catalytic activityof the cyclic guanidine.

In certain embodiments, each ring in the cyclic guanidine is comprisedof ≥5-members. For instance, the cyclic guanidine may be a 5-memberring, a 6-member ring, or a 7-member ring. As used herein, the term“member” refers to an atom located in a ring structure. Accordingly, a5-member ring will have 5 atoms in the ring structure (“a” and/or “b”=1in structures (V)-(VIII)), a 6-member ring will have 6 atoms in the ringstructure (“a” and/or “b”=2 in structures (V)-(VIII)), and a 7-memberring will have 7 atoms in the ring structure (“a” and/or “b”=3 instructures (V)-(VIII)) It will be appreciated that if the cyclicguanidine is comprised of ≥2 rings (e.g., structures (VII) and (VIII),the number of members in each ring of the cyclic guanidine can either bethe same or different. For example, one ring may be a five-member ringwhile the other ring may be a six-member ring. If the cyclic guanidineis comprised of ≥3 rings, then in addition to the combinations cited inthe preceding sentence, the number of members in a first ring of thecyclic guanidine can be different from the number of members in anyother ring of the cyclic guanidine.

Moreover, in some embodiments, the cyclic guanidine can either besubstituted or unsubstituted. For example, as used herein in conjunctionwith the cyclic guanidine, “substituted”, in certain embodiments, refersto a cyclic guanidine wherein R₂₅, R₂₆, and/or R₂₇ of structures (V)and/or (VI) and/or R₂₉ of structures (VII) and/or (VIII) is nothydrogen. As used herein in conjunction with the cyclic guanidine,“unsubstituted”, in certain embodiments, refers to a cyclic guanidinewherein R₂₁-R₂₇ of structures (V) and/or (VI) and/or R₂₁-R₂₉ ofstructures (VII) and/or (VIII) is hydrogen. In some embodiments, thesubstituted cyclic guanidine is 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

In certain embodiments, the metal amidine complex comprises acarboxylate derived from a carboxylic acid of the following formula:

wherein R₁₁ is hydrogen, C₁-C₂₅ alkyl, C₂-C₂₅ alkyl interrupted byoxygen or sulfur; C₂-C24 alkenyl, C₄-C₁₅ cycloalkyl which isunsubstituted or substituted by C₁-C₄ allyl and/or carboxyl; C₅-C₁₅cycloalkenyl which is unsubstituted or substituted by C₁-C₄ alkyl and/orcarboxyl; C₁₃-C₂₆ polycycloalkyl, C₇-C₉ phenylalkyl which isunsubstituted or substituted on the phenyl ring by C₁-C₄ alkyl; —COR₁₆,a 5- or 6-membered heterocyclic ring which is unsubstituted orsubstituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen or carboxyl; a 5- or6-membered heterocyclic ring which is benzo-fused and is unsubstitutedor substituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen or carboxyl; or aradical of one of the following formulae:

wherein R₁₂, R₁₃, R₁₄ and R₁₅ independently are hydrogen, hydroxyl,C₁-C₁₈ alkoxy, C₂-C₁₈ alkoxy which is interrupted by oxygen or sulfur;C₁-C₂₅ alkyl, C₂-C₂₅ alkyl which is interrupted by oxygen or sulfur;C₂-C₂₄ alkenyl, C₅-C₁₅ cycloalkyl which is unsubstituted or substitutedby C₁-C₄ alkyl; C₅-C₁₅ cycloalkenyl which is unsubstituted orsubstituted by C₁-C₄ alkyl; phenyl or naphthyl which is unsubstituted orsubstituted by C₁-C₄ alkyl; C₇-C₉ phenylalkyl which is unsubstituted orsubstituted on the phenyl ring by C₁-C₄ alkyl; C₁₀-C₁₂ naphthylalkylwhich is unsubstituted or substituted on the naphthyl ring system byC₁-C₄ alkyl; or are —COR₆, with the proviso that, if one of the radicalsR₁₂, R₁₃, R₁₄ and R₁₅ is hydroxyl, the other radical attached to thesame carbon atom is other than hydroxyl; or else R₁₂ and R₁₃ or R₁₄ andR₁₅, together with the carbon atom to which they are attached, form anunsubstituted or C₁-C₄ alkyl-substituted C₅-C₁₂ cycloalkylidene ring;wherein R₁₆ is hydroxyl, C₁-C₁₈ alkoxy, or C₂-C₁₈ alkoxy which isinterrupted by oxygen or sulfur; or

wherein R₃₇, R₃₈, R₃₉, R₄₀ and R₄₁ are independently hydrogen, hydroxyl,halogen, nitro, cyano, CF₃, —COR₆, C₁-C₂₅ alkyl, C₂-C₂₅ alkyl which isinterrupted by oxygen or sulfur; C₁-C₂₅ haloalkyl, C₁-C₁₈ alkoxy, C₂-C₁₈alkoxy which is interrupted by oxygen or sulfur; C₁-C₁₈ alkylthio,C₂-C₂₄ alkenyl, C₅-C₁₅ cycloalkyl which is unsubstituted or substitutedby C₁-C₄ alkyl; C₅-C₁₅ cycloalkenyl which is unsubstituted orsubstituted by C₁-C₄ alkyl; phenyl or naphthyl which is unsubstituted orsubstituted by C₁-C₄ alkyl; C₇-C₉ phenylalkyl which is unsubstituted orsubstituted on the phenyl ring by C₁-C₄ alkyl; C₁₀-C₁₂ naphthylalkylwhich is unsubstituted or substituted on the naphthyl ring system byC₁-C₄ alkyl; phenoxy or naphthoxy which is unsubstituted or substitutedby C₁-C₄ alkyl; C₇-C₉ phenylalkoxy which is unsubstituted or substitutedon the phenyl ring by C₁-C₄ alkyl; C₁₀-C₁₂ naphthylalkoxy which isunsubstituted or substituted on the naphthyl ring system by C₁-C₄ alkyl;or else the radicals R₃₈ and R₃₉ or the radicals R₃₉ and R₄₀ or theradicals R₄₀ and R₄₁ or the radicals R₃₇ and R₄₁, together with thecarbon atoms to which they are attached, form an unsubstituted or C₁-C₄alkyl-, halogen- or C₁-C₄ alkoxy-substituted benzo ring, with theproviso that at least one of the radicals R₃₇, R₃₈, R₃₉, R₄₀ and R₄₁ ishydrogen;R₄₂ is hydroxyl, halogen, nitro, cyano, CF₃, C₁-C₂₅ alkyl, C₂-C₂₅ alkylwhich is interrupted by oxygen or sulfur; C₁-C₂₅ haloalkyl, C₁-C₁₈alkoxy, C₂-C₁₈ alkoxy which is interrupted by oxygen or sulfur; C₁-C₁₈alkylthio or C₂-C₂₄ alkenyl;R₄₃ and R₄₄ are independently hydrogen, C₁-C₂₅ alkyl, C₁-C₁₈ alkoxy or—Y—(CH₂)_(s)COR₆;R₄₅ and R₄₆ are independently hydrogen, C₁-C₂₅ alkyl, C₃-C₂₅ alkyl whichis interrupted by oxygen or sulfur; C₂-C₂₄ alkenyl, C₅-C₁₅ cycloalkylwhich is unsubstituted or substituted by C₁-C₄ alkyl; phenyl or naphthylwhich is unsubstituted or substituted by C₁-C₄ alkyl;X₁₁ is a direct bond, oxygen, sulfur, C(O), C₁-C₁₈ alkylene, C₂-C₁₈alkylene which is interrupted by oxygen or sulfur; C₂-C₁₈ alkenylene,C₂-C₁₈ alkynylene, C₂-C₂₀ alkylidene, C₇-C₂₀ phenylalkylidene or C₅-C₈cycloalkylene, with the proviso that, if m and n are 0, X₁₁ is otherthan oxygen and sulfur;Y is oxygen or

R_(a) is hydrogen or C₁-C₈ alkyl;e and f independently of one another are integers from 0 to 10, p is aninteger from 0 to 4, and s is an integer from 1 to 8. In certainembodiments, the carbon/late of the metal amidine complex is formate,acetate, 2-ethylhexanoate, or neodecanoate.

In certain embodiments, the metal amidine complex is one as described inU.S. Pat. No. 7,485,729 to Hsieh et al, herein incorporated by referencein its entirety. Procedures for preparing the metal amidine complexesherein can be found at cols. 21-22 and Table 2 of U.S. Pat. No.7,485,729, specifically incorporated herein by reference.

In certain embodiments, the metal of the catalyst composition ismercury, bismuth, barium, zinc, calcium, cadmium, zirconium, aluminum,nickel, manganese, vanadium, iron, cerium, thorium, cobalt, copper,titanium, hafnium, lithium, lead, or potassium. In particularembodiments, the metal of the metal compound is zinc or bismuth. Incertain embodiments, the metal is comprised by a metal carboxylate.

In certain embodiments the amine carboxylate salt useful in thisdisclosure is derived from one or more amine selected from aliphaticprimary amines such as methylamine, ethylamine, propylamine,isopropylamine, butylamine, amylamine, hexylamine, octylamine,2-ethylhexylamine, nonylamine, decylamine, oleylamine, laurylamine,pentadecylamine, cetylamine, stearylamine, cyclohexylamine and the like;aliphatic secondary amines such as dimethylamine, diethylamine,dipropylamine, diisopropylamine, dibutylamine, diamylamine,dihexylamine, dioctylamine, di(2-ethylhexyl)amine, didecylamine,dilaurylamine, dicetylamine, distearylamine, methylstearylamine,ethylstearylamine, butylstearylamine and the like; aliphatic tertiaryamines such as triamylamine, trihexylamine, trioctylamine,ethyldiisopropylamine and the like; aliphatic unsaturated amines such astriallylamine, oleylamine and the like; alicyclic amines such asmenthane diamine, isophorone diamine, norbornane diamine, piperidine,N,N′-dimethylpiperidine, N-aminoethylpiperidine, 1,2-diaminocyclohexane,bis(4-amino-3-methylcyclohexyl)methane, bis(4-aminocyclohexyl)methane,polycyclohexyl polyamine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU),1,4-diazabicyclo(2,2,2)octane (DABCO),1,5-diazabicyclo[4,3,0]nonene-5(DBN),6-dibutylamino-1,8-diazabicyclo[5,4,0]undecene-7,N,N-dimethylcyclohexylamine, 1,2-bis(dimethylamino)cyclohexane,1,4-bis(dimethylamino)cyclohexane,N,N,N′,N′-tetramethylisophoronediamine,N,N,N′,N′-tetramethylnorbornanediamine,bis(4-dimethylaminocyclohexyl)methane,bis(4-dimethylamino-3-methylcyclohexyl)methane, aziridine and the like;aromatic amines such as meta-phenylenediamine,4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone,N,N,N′,N′-tetramethyl-1,4-phenylenediamine, N,N-dimethylbenzylamine,α-methylbenzyldimethylamine; aniline, laurylaniline, stearylaniline,triphenylamine and the like; aliphatic aromatic amines such asbenzylamine, m-xylylenediamine, benzyldimethylamine,2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimetylaminomethyl)phenol;ether functional amines such as 3-methoxypropylamine,3-lauryloxypropylamine,3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane (ATU),morpholine, N-methylmorpholine, polyoxypropylene diamine,polyoxypropylene triamine, polyoxyethylene diamine; polyamide aminessuch as polyamide obtained by reaction of dimer acid with a polyaminesuch as diethylenetriamine or triethylenetetraamine, polyamide from theother polycarboxylic acids, polyoxypropylene amines such aspolyoxypropylene diamine, polyoxypropylene triamine; phenols; modifiedamines such as epoxy-modified amine obtained by reaction of the aboveamines with an epoxy compound, Mannich-modified amine obtained byreaction of the above amines with formalin and phenols, Michaeladdition-modified amine, ketimine and heterocyclic amines such aspyridine, 2-aminopyridine, 2-(dimethylamino)pyridine,4-(dimethylaminopyridine), 2-hydroxypyridine, imidazole,2-ethyl-4-methylimidazole, morpholine, N-methylmorpholine, piperidine,2-piperidinemethanol, 2-(2-piperidino)ethanol, piperidone, dicyandiamideand other hydroxyl functional amines such as monoethanolamine,diethanolamine, triethanolamine, 3-hydroxypropylamine,2-(2-aminoethylamino)ethanol, dimethylamino-2-propanol,diethylamino-2-propanol, dimethylamino ethanol, diethylamino ethanol,2-dimethylamino-2-methyl-1-propanol, and diamines such asN-methyl-1,3-propanediamine, N,N′-dimethyl-1,3-propanediamine,ethylenediamine, propylenediamine, diethylenetriamine,triethylenetetramine, tetraethylenepentamine, hexamethylenediamine,methylpentamethylenediamine, trimethylhexamethylenediamine, guanidine,N,N,N′,N′-tetramethylethylenediamine,N,N,N′,N′-tetramethyl-1,3-diaminopropane,N,N,N′,N′-tetramethyl-1,4-diaminobutane,N,N,N′,N′-tetramethyl-1,6-diaminohexane, diethylaminopropylamine,dimethylaminopropylamine, 3-dimethylaminopropylamine,3-diethylaminopropylamine, 3-butylaminopropylamine,3-morpholinopropylamine, 2-(1-piperazinyl)ethylamine, guanidine,tetramethyl guanidine, diphenylguanidine, aryl-substituted biguanidessuch as 1-o-tolylbiguanide, 1-phenylbiguanide and the like,2,4,6-tris(dimethylaminomethyl)phenol and the like. The amine compoundis not limited thereto.

In certain embodiments the amine compound of the amine carboxylate saltis an amidine of formulae I-VIII described above.

As specific examples of amidine compounds useful in the currentdisclosure are 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine,1-ethyl-2-methyl-1,4,5,6-tetrahydropyrimidine,1,2-diethyl-1,4,5,6-tetrahydropyrimidine,1-n-propyl-2-methyl-1,4,5,6-tetrahydropyrimidine,1-isopropyl-2-methyl-1,4,5,6-tetrahydropyrimidine,1-ethyl-2-n-propyl-1,4,5,6-tetrahydropyrimidine and1-ethyl-2-isopropyl-1,4,5,6-tetrahydropyrimidine; guanidine compoundssuch as 1-methylguanidine, 1-n-butylguanidine, 1,1-dimethylguanidine,1,1-diethylguanidine, 1,1,2-trimethylguanidine,1,2,3-trimethylguanidine, 1,1,3,3-tetramethylguanidine,1,1,2,3,3-pentamethylguanidine, 2-ethyl-1,1,3,3-tetramethylguanidine,1,1,3,3-tetramethyl-2-n-propylguanidine,1,1,3,3-tetramethyl-2-isopropylguanidine,2-n-butyl-1,1,3,3-tetramethylguanidine,2-tert-butyl-1,1,3,3-tetramethylguanidine, 1,2,3-tricyclohexylguanidine,1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-ethyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-n-propyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-isopropyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-n-butyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-isobutyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-tert-butyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7cyclohexyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-n-octyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-2-ethylhexyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene and7-decyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene; and biguanide compound suchas biguanide, 1-methylbiguanide, 1-n-butylbiguanide,1-(2-ethylhexyl)biguanide, 1-n-octadecylbiguanide,1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide,1-allylbiguanide, 1-n-butyl-N2-ethylbiguanide,1,1′-ethylenebisbiguanide, 1-[3-(diethylamino)propyl]biguanide,1-[3-(dibutylamino)propyl]biguanide andN′,N″-dihexyl-3,12-diimino-2,4,11,13-tetraazatetradecanediamidine. Theseamine compounds may be used singly or two or more of them may be used incombination.

Among them, 2-(dimethylamino) pyridine, 4-(dimethylamino) pyridine,2-hydroxypyridine, imidazole, DBU, DBN, DABCO, and other heterocycliccompounds are preferred since they exhibit a high activity. DBU and DBNare more preferred. Aryl-substituted biguanides are also preferred sincethey exhibit a high adhesiveness.

In certain embodiments the amine carbon/late may be derived from anamine of general formulaR⁵¹ _(d)YR⁵²NHR⁵³wherein Y is one selected from O, N, S and P; when Y is O or S, d is 1and when Y is N or P, d is 2; R⁵¹ are each a hydrogen atom, or asubstituted or unsubstituted hydrocarbon group having 1 to 20 carbonatoms; when the number of R⁵¹ is two, R⁵¹ may be the same or different;R⁵² is a substituted or unsubstituted bivalent hydrocarbon group having1 to 10 carbon atoms; and R⁵³ is a hydrogen atom or a methyl group. Inparticular, monoethanolamine, 3-hydroxypropylamine,2-(2-aminoethylamino)ethanol, dimethylamino-2-propanol,diethylamino-2-propanol, dimethylamino ethanol, diethylamino ethanol,2-dimethylamino-2-methyl-1-propanol ethylenediamine,N-methylethylenediamine, 1,3-propanediamine,N-methyl-1,3-propanediamine, N,N′-dimethyl-1,3-propanediamine,diethylaminopropyl amine, dimethylaminopropyl amine anddiethylenetriamine can be used.

In certain embodiments a phenyl guanidine of the structure below couldbe used in the preparation of the amine carboxylate salt;

wherein, each R¹ is independently hydrogen or a hydrocarbon group inwhich the carbon atom at position 1 is saturated; each R² isindependently hydrogen, a halogen, hydroxyl group, amino group, nitrogroup, a cyano group, sulfonic acid group or an organic group, and a isan integer of 0 to 5.

Phenyl guanidines with a 2-methylphenyl group, a 3-methylphenyl group, a4-methylphenyl group, a 4-aminophenyl group or a 4-guanidinophenyl groupmay be used, in many embodiments a phenyl guanidine having unsubstitutedphenyl or 2-methylphenyl group are employed as they are readilyavailable and enhance the surface curability of the organic polymer (A)and provide cured products exhibit good adhesiveness.

A ketimine which generates an amine compound by hydrolysis can also beused as an amine precursor to the amine carboxylate salt of the silanolcondensation catalyst of the present disclosure.

The carboxylate of the amine carboxylate salt may a carboxylate asdescribed above for amidine complexes comprising a carboxylate, but arenot limited thereto. Specific examples of carboxylic acid which can usedtogether with an amine compound include straight chain saturated fattyacids such as acetic acid, propionic acid, butyric acid, valeric acid,caproic acid, enanthic acid, caprylic acid, 2-ethylhexanoic acid,pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoicacid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoicacid, stearic acid, nonadecanoic acid, arachic acid, behenic acid,lignoceric acid, cerotic acid, montanic acid, melissic acid, laccericacid and the like; monoene unsaturated fatty acids such as undecylenicacid, linderic acid, tsuzuic acid, physeteric acid, myristoleic acid,2-hexadecenoic acid, 6-hexadecenoic acid, 7-hexadecenoic acid,palmitoleic acid, petroselic acid, oleic acid, elaidic acid, asclepinicacid, vaccenic acid, gadoleic acid, gondoic acid, cetoleic acid, erucicacid, brassidic acid, selacholeic acid, ximenic acid, lumequeic acid,acrylic acid, methacrylic acid, angelic acid, crotonic acid, isocrotonicacid, 10-undecenoic acid and the like; polyene unsaturated fatty acidssuch as linoelaidic acid, linoleic acid, 10,12-octadecadienoic acid,hiragoic acid, alpha-eleostearic acid, beta-eleostearic acid, punicicacid, linolenic acid, 8,11,14-eicosatrienoic acid,7,10,13-docosatrienoic acid, 4,8,11,14-hexadecatetraenoic acid, morocticacid, stearidonic acid, arachidonic acid, 8,12,16,19-docosatetraenoicacid, 4,8,12,15,18-eicosapentaenoic acid, clupanodonic acid, nishinicacid, docosahexaenoic acid and the like; branched fatty acids such as1-methylbutyric acid, isobutyric acid, 2-ethylbutyric acid, isovalericacid, tuberculostearic acid, pivalic acid, 2,2-dimethylbutyric acid,2-ethyl-2-methylbutyric acid, 2,2-diethylbutyric acid,2,2-dimethylvaleric acid, 2-ethyl-2-methylvaleric acid,2,2-diethylvaleric acid, 2,2-dimethylhexanoic acid, 2,2-diethylhexanoicacid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid,neodecanoic acid, versatic acid and the like; fatty acids having atriple bond such as propiolic acid, tariric acid, stearolic acid,crepenynic acid, ximenynic acid, 7-hexadecynoic acid and the like;alicyclic carboxylic acids such as naphthenic acid, malvalic acid,sterculic acid, hydnocarpic acid, chaulmoogric acid, gorlic acid,1-methylcyclopentanecarboxylic acid, 1-methylcyclohexanecarboxylic acid,2-methylbicyclo[2.2.1]-5-heptene-2-carboxylic acid,1-adamantanecarboxylic acid, bicycle[2.2.1]heptane-1-carboxylic acid,bicycle[2.2.2]octane-1-carboxylic acid and the like; oxygen containingfatty acids such as acetoacetic acid, ethoxy acetic acid, glyoxylicacid, glycolic acid, gluconic acid, sabinic acid, 2-hydroxytetradecanoicacid, ipurolic acid, 2,2-dimethyl-3-hydroxypropionic acid,2-hydroxyhexadecanoic acid, jalapinolic acid, juniperic acid,ambrettolic acid, aleuritic acid, 2-hydroxyoctadecanoic acid,12-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid,9,10-dihydroxyoctadecanoic acid, ricinoleic acid, camlolenic acid,licanic acid, pheronic acid, cerebronic acid,2-methyl-7-oxabicyclo[2.2.1]-5-heptene-2-carboxylic acid and the like;and halogen substituted monocarboxylic acids such as chloroacetic acid,2-chloroacrylic acid and chlorobenzoic acid. Examples of aliphaticdicarboxylic acids include saturated dicarboxylic acids such as adipicacid, azelaic acid, pimelic acid, suberic acid, sebacic acid,ethylmalonic acid, glutaric acid, oxalic acid, malonic acid, succinicacid, oxydiacetic acid, dimethylmalonic acid, ethylmethylmalonic acid,diethylmalonic acid, 2,2-dimethylsuccinic acid, 2,2-diethylsuccinicacid, 2,2-dimethylglutaric acid,1,2,2-trimethyl-1,3-cyclopentanedicarboxylic acid; and unsatureateddicarboxylic acids such as maleic acid, fumaric acid,acetylenedicarboxylic acid and itaconic acid. Examples of aliphaticpolycarboxylic acids include tricarboxylic acids such as aconitic acid,4,4-dimethylaconitic acid, citric acid, isocitric acid,3-methylisocitric acid and the like. Examples of aromatic carboxylicacids include aromatic monocarboxylic acids such as benzoic acid,9-anthracenecarboxylic acid, atrolactic acid, anisic acid,isopropylbenzoic acid, salicylic acid and toluic acid; and aromaticpolycarboxylic acids such as phthalic acid, isophthalic acid,terephthalic acid, carboxyphenylacetic acid, pyromellitic acid and thelike.

Typically, the acid employed in the amine carboxylate is amonocarboxylic acid, for example a linear monocarboxylic acid due togood compatibility with the silane functional polymers. When the meltingpoint of a carboxylic acid is high the handling thereof can becomedifficult. Accordingly, the melting point of the carboxylic acid usedtogether with the amine compound in the silanol condensation catalyst istypically 65° C. or lower, for example from −50 to 50° C., often from−40 to 35° C.

Typically, the number of carbon atoms in the carboxylic acid is from 5to 20, for example from 6 to 18, often from 8 to 12. If the number ofthe carbon atoms too large the carboxylic acids are solids, which canrender them incompatible with silane functional polymers. On the otherhand, if the number of the carbon atoms is too small the volatility ofthe carboxylic acid becomes high so that odor tends to increase.

In many embodiments, due in part to availability and workability, thecarboxylate is derived from 2-ethylhexanoic acid, octanoic acid, oleicacid, naphthenic acid, 2,2-dimethyloctanoic acid,2-ethyl-2,5-dimethylhexanoic acid, neodecanoic acid, versatic acid andthe like.

In certain embodiment the catalyst composition may comprise from about 1to about 99% of the amine carboxylate and from about 1 to 99% of metalamidine complex; in another embodiment from about 1 to about 20% ofmetal amidine complex and from about 10 to 99% of the amine carboxylate.

In certain embodiments, the catalyst composition comprises a mixture ofat least one metal amidine complex and at least one amine carboxylate,and excess free carboxylic acid. In certain embodiments, the molar ratioof carboxylic acid used is from about 1.0 to 10.0 per mole of amine, ormore preferably from about 1.0 to 4.0 per mole of amine.

The inventors have unexpectedly found that amidine complexes incombination with carboxylate salts of various amines either on its ownor in combination with certain adhesion promoter components and/oracidic compounds exhibit curing behavior similar to or even better thanorganotin compounds, and are therefore suitable as replacements fororganotin catalysts in compositions having a reactive silyl-terminatedpolymer that can undergo condensation reactions such as in RTV-1 sealantand RTV-2 formulations.

Curable compositions using selected amidine complexes in combinationwith amine carboxylates compounds or a combination thereof may alsoexhibit certain storage stability of the uncured composition in thecartridge, adhesion onto several surfaces, and a cure rate in apredictable time scheme.

Thus, many embodiments of the disclosure provided a curable compositionexhibiting a relatively short tack-free time, curing through the bulk,as well as long storage stability in the cartridge, i.e., in the absenceof humidity.

For example, one embodiment provides a curable composition, comprising:

(A) one or more organic polymers having a reactive-silicon-containinggroup, and

(B) a silanol condensation catalyst consisting of one or more metalamidine complexes and one or more amine carboxylate salts,

wherein at least one part of the reactive-silicon-containing group(s) ofthe organic polymer(s) (A) is represented by the following generalformula:—(CR² ₂)₂—(SiR¹ _(2-a)X_(a))_(m)—SiX₃  (1)wherein each R¹ independently represents a substituted or unsubstitutedhydrocarbon group having 1 to 20 carbon atoms, or a triorganosiloxygroup represented by (R′)₃SiO— wherein R′s are each a substituted orunsubstituted hydrocarbon group having 1 to 20 carbon atoms, and R′s maybe the same or different, each R² are independently a hydrogen atom, ora substituted or unsubstituted hydrocarbon group having 1 to 10 carbonatoms, each X are independently a hydroxyl group, or a hydrolyzablegroup, a is 0, 1 or 2, and m is 0 or an integer of from 1 to 19.

For example, in certain embodiments X is an alkoxy group, e.g., amethoxy group.

In many embodiments the ratio of the organic polymer having the grouprepresented by the general formula (1) in the organic polymer(s) of thecomponent (A) in the curable composition of the disclosure is 10% ormore by weight.

Many embodiments is provide a curable composition wherein the main chainskeleton of the organic polymer(s) of the component (A) is at least onepolymer selected from the group consisting of polyoxyalkylene polymers,saturated hydrocarbon polymers, and (meth)acrylic acid ester polymers.In certain embodiments the polyoxyalkylene polymers are polyoxypropylenepolymers.

In many embodiments the silanol condensation catalyst is present in anamount of 0.001 to 20 parts by weight for 100 parts by weight of theorganic polymer(s) (A).

In certain embodiments the curable composition of the disclosure furthercomprises a silane coupling agent (C), typically in an amount of 0.01 to20 parts by weight for 100 parts by weight of the organic polymer(s)(A).

Certain embodiments are to a one-part type curable compositioncomprising the curable composition of the disclosure.

One particular embodiment provides a sealant comprising the curablecomposition of the disclosure.

One particular embodiment provides an adhesive comprising the curablecomposition of the disclosure.

Example of silane coupling agents useful in the disclosure includeisocyanate silanes such as γ-isocyanate propyltrimethoxysilane,γ-isocyanate propyltriethoxysilane, γ-isocyanatepropylmethyldiethoxysilane, γ-isocyanate propylmethyldimethoxysilane,(isocyanatemethyl) trimethoxysilane, (isocyanatemethyl)dimethoxymethylsilane and the like; ketimine type silanes such asN-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propaneamine and thelike; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane,γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane,γ-mercaptopropylmethyldiethoxysilane, mercaptomethyltriethoxysilane andthe like; carboxysilanes such as β-carboxyethyltriethoxysilane,β-carboxyethylphenylbis(2-methoxyethoxy)silane,N-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane and thelike; vinyl-type-unsaturated-group-containing silanes such asvinyltrimethoxysilane, vinyltriethoxysilane,γ-methacryloyloxypropylmethyldimethoxy silane,γ-acryloyloxypropyltriethoxysilane and the like; halogen-containingsilanes such as γ-chloropropyltrimethoxysilane and the like; andisocyanurate silanes such as tris(3-trimethoxysilylpropyl) isocyanurateand the like, and the like. A reactant of an aminosilane and anisocyanate silane as described above, a reactant of an aminosilane and a(meth)acryloyloxy-group-containing silane, or the like can also be used.Condensation products obtained by condensing the above-mentioned silanespartially can also be used. Furthermore, derivatives obtained bymodifying these can also be used as the silane coupling agent, examplesof the derivatives including amino-modified silyl polymers, sililatedaminopolymers, unsaturated aminosilane complexes, phenylamino long-chainalkylsilanes, aminosililated silicones, and sililated polyesters.

Certain embodiments provide a composition for forming a cured polymercomposition comprising (A) a polymer having at least a reactivesilylgroup; (B) about 0.01-7 parts per weight per 100 parts per weightof the polymer (A) of the above silanol condensation catalyst; (C) acoupling agent, crosslinker or chain extender chosen from analkoxysilane, an alkoxysiloxane, an oximosilane, an oximosiloxane, anenoxysilane, an enoxysiloxane, an aminosilane, a carboxysilane, acarboxysiloxane, an alkylamidosilane, an alkylamidosiloxane, anarylamidosilane, an arylamidosiloxane, an alkoxyaminosilane, analkaryaminosiloxane, an alkoxycarbamatosilane, analkoxycarbamatosiloxane, and combinations of two or more thereof; (D) atleast one adhesion promoter chosen from a silane or siloxane other thanthe compounds listed under (C); (E) optionally, a filler component; and(F) optionally at least one acidic compound chosen from a phosphateester, a phosphonate, a phosphite, a phosphine, a sulfite, apseudohalogenide, a branched C₄-C₃₀-alkyl carboxylic acid or acombination of two or more thereof.

In certain embodiments, the polymer component (A₁) has the formula:R² _(3-a)R¹ _(a)Si—Z—[R₂SiO]_(x)[R¹ ₂SiO]_(y)—Z—SiR¹ _(a)R² _(3-a)wherein x is 0 to 10000; y is 0 to 1000; a is 0 to 2; and R is methyl.In another aspect, R¹ is chosen from a C₁-C₁₀-alkyl, a C₁-C₁₀alkylsubstituted with one or more of Cl, F, N, O or S, a phenyl, a C₇-C₁₆alkylaryl, a C₇-C₁₆ arylalkyl, a C₂-C₄ polyalkylene ether, or acombination of two or more thereof, and other siloxane units may bepresent in amounts less than 10 mol % such as methyl, vinyl, phenyl. Inyet another embodiment, R² is chosen from OH, a C₁-C₈-alkoxy, aC₂-C₁₈-alkoxyalkyl, an oximoalkyl, an enoxyalkyl, an aminoalkyl, acarboxyalkyl, an amidoalkyl, an amidoaryl, a carbamatoalkyl, or acombination of two or more thereof, and Z is —O—, bond, or —C₂H₄—.

In certain embodiments the crosslinker component (C) is chosen fromtetraethylorthosilicate (TEOS), a polycondensate of TEOS,methyltrimethoxysilane (MTMS), vinyl-trimethoxysilane,methylvinyldimethoxysilane, dimethyldiethoxysilane,vinyltriethoxysilane, tetra-n-propylorthosilicate,vinyltris(methylethylketoxime)silane,methyltris(methylethylketoxime)silane, trisacetamidomethylsilane,bisacetamidodimethylsilane, tris(N-methyl-acetamido)methylsilane,bis(N-methylacetamido)dimethylsilane,(N-methyl-acetamido)methyldialkoxysilane, trisbenzamidomethylsilane,trispropenoxymethylsilane, alkyldialkoxyamidosilanes,alkylalkoxybisamidosilanes, CH₃Si(OC₂H₅)₁₋₂(NHCOR)₂₋₁,(CH₃Si(OC₂H₅)(NCH₃COC₆H₅)₂, CH₃Si(OC₂H₅)—(NHCOC₆H₅)₂,methyldimethoxy(ethylmethyl-ketoximo)silane;methylmethoxybis-(ethylmethylketoximo)silane;methyldimethoxy(acetal-doximo)silane;methyldimethoxy(N-methylcarbamato)silane;ethyldimethoxy(N-methyl-carbamato)silane;methyldimethoxyisopropenoxysilane; trimethoxyisopropenoxysilane;methyltri-isopropenoxysilane; methyldimethoxy(but-2-ene-2-oxy)silane;methyldimethoxy(1-phenylethenoxy)silane;methyldimethoxy-2(1-carboethoxypropenoxy)silane;methylmethoxydi-N-methylaminosilane; vinyldimethoxymethylaminosilane;tetra-N,N-diethylaminosilane; methyldimethoxymethylaminosilane;methyltricyclohexylaminosilane; methyldimethoxy-ethylaminosilane;dimethyldi-N,N-dimethylaminosilane; methyldimethoxyisopropylaminosilanedimethyldi-N,N-diethylaminosilane;ethyldimethoxy(N-ethylpropionamido)silane;methyldi-methoxy(N-methylacetamido)silane;methyltris(N-methylacetamido)silane;ethyldimethoxy(N-methylacetamido)silane;methyltris(N-methylbenzamido)silane;methylmethoxybis(N-methylacetamido)silane;methyldimethoxy(caprolactamo)silane;trimethoxy(N-methylacetamido)silane;methyldimethoxyethylacetimidatosilane;methyldimethoxypropylacetimidatosilane;methyldimethoxy(N,N′,N′-trimethylureido)silane;methyldimethoxy(N-allyl-N′,N′-dimethylureido)silane;methyldimethoxy(N-phenyl-N′,N′-dimethylureido)silane;methyldimethoxyisocyanatosilane; dimethoxydiisocyanatosilane;methyldimethoxythioisocyanatosilane;methylmethoxydithioisocyanatosilane, or a combination of two or morethereof.

According to one embodiment, the composition comprises about 1 to about10 wt. of the crosslinker component (C) based on 100 wt. % of thepolymer component (A).

In certain embodiments, the adhesion promoter component (D) is chosenfrom an aminoalkyltrialkoxysilane, an aminoalkylalkyldialkoxysilane, abis(alkyltrialkoxy-silyl)amine, a tris(alkyltrialkoxysilyl)amine, atris(alkyltrialkoxy-silyl)cyanuarate, and atris-(alkyl-trialkoxy-silyl)isocyanuarate, or a combination of two ormore thereof.

According to one embodiment, the component (F) is chosen from a monoester of a phosphate; a phosphonate of the formula (R₃O)PO(OH)₂,(R₃O)P(OH)₂, or R₃P(O)(OH)₂ where R₃ is a C₁-C₁₈-alkyl, aC₂-C₂₀-alkoxyalkyl, phenyl, a C₇-C₁₂-alkylaryl, apoly(C₂-C₄-alkylene)oxide ester or its mixtures with diesters; abranched alkyl C₄-C₁₄-alkyl carboxylic acid; or a combination of two ormore thereof.

According to one embodiment, the crosslinker component (C) is chosenfrom a silane or a siloxane, the silane or siloxane having two or morereactive groups that can undergo hydrolysis and/or condensation reactionwith polymer (A) or on its own in the presence of water and component(F).

According to one embodiment, the polymer component (A) is chosen from apolyorganosiloxane comprising divalent units of the formula [R₂SiO] inthe backbone, wherein R is chosen from a C₁-C₁₀-alkyl; a C₁-C₁₀ alkylsubstituted with one or more of Cl, F, N, O or S; a phenyl; a C₇-C₁₆alkylaryl; a C₇-C₁₆ arylalkyl; a C₂-C₄ polyalkylene ether; or acombination of two or more thereof.

According to one embodiment, the catalyst (B) is present in an amount offrom about 0.0.025 to about 0.7 parts per weight per 100 pt. wt. ofcomponent (A).

According to one embodiment, the component (F) is present in an amountof from about 0.02 to about 3 part per 100 parts of component (A).

According to one embodiment, the composition comprises 100 parts ofcomponent (A), 0.01 to about 7 parts of a catalyst (B), 0.1 to about 10parts of at least one crosslinker (C), 0.1 to about 5 parts of anadhesion promoter (D), 0 to about 300 parts of component (E), 0.01 toabout 8 parts of component (F) whereby this composition can be stored inthe absence of humidity and is curable in the presence of humidity uponexposure to ambient air.

According to one embodiment, the composition is a two-part compositioncomprising: (i) a first portion comprising the polymer component (A),optionally the filler component (E), and optionally the acidic compound(F₁; and (ii) a second portion comprising the crosslinker (C), thecatalyst component (B), the adhesive promoter (D), and the acidiccompound (F), whereby (i) and (ii) are stored separately until appliedfor curing by mixing of the components (i) and (ii).

According to one embodiment, portion (i) comprises 100% wt. of component(A), and 0 to 70 parts of component (E); and portion (ii) comprises 0.1to 10 parts of at least one crosslinker (C), 0.01 to 7 parts of acatalyst (B), 0 to 5 parts of an adhesion promoter (D), and 0.02 to 3parts component (F).

In another aspect, the present disclosure provides a method of providinga cured material comprising exposing the composition to ambient air.

According to one embodiment, a method of providing a cured materialcomprises combining the first portion and the second portion and curingthe mixture.

According to one embodiment, the composition is stored in a sealedcartridge or flexible bag having outlet nozzles for extrusion and/orshaping of the uncured composition prior to cure.

In still another aspect, the present disclosure provides a cured polymermaterial formed from the composition.

According to one embodiment, the cured polymer material is in the formof an elastomeric or duromeric seal, an adhesive, a coating includingantifouling coating, an encapsulant, a shaped article, a mold, and animpression material.

The compositions are found to exhibit good storage stability and adhereto a variety of surfaces. In one embodiment, the curable compositionsexhibit excellent adherence to thermoplastic surfaces, includingpolyacrylate and polymethylmethacrylate (PMMA) surfaces.

Further according to the disclosure, there is provided a silanolcondensation catalyst consisting of one or more metal amidine complexesand one or more amine carboxylate salts. Yet further according to thedisclosure, there is provided a silanol condensation catalyst consistingessentially of one or more metal amidine complexes and one or more aminecarboxylate salts. In the latter, the catalyst does not containadditional substances that change the essential features of thecatalyst.

DETAILED DESCRIPTION OF THE DISCLOSURE

In accordance with the present disclosure is provided a compositioncomprising a metal amidine complex in combination with amine carboxylatesalts that are useful as catalysts for polymerization reactions of oneor more organic polymers having a reactive-silicon-containing group.

In certain embodiments, the amidine of the metal amidine complex has theformula

wherein R¹ is hydrogen, alkyl of 1 to 25 carbon atoms, an amine groupwhich can be substituted, for example by an optionally substitutedhydrocarbyl group, or a hydroxyl group which can be etherified, forexample with an optionally substituted hydrocarbyl group having up to 8carbon atoms; R² and R³ each independently represent hydrogen or anorganic group attached through a carbon atom or are joined to oneanother to form with the linking —N═C—N— a heterocyclic ring or a fusedbicyclic ring with one or more heteroatoms, and R⁴ represents hydrogen,an organic group attached through a carbon atom or a hydroxy group whichcan be etherified, for example with an optionally substitutedhydrocarbyl group having up to 8 carbon atoms. When R¹ or R⁴ is anorganic group it can for example contain 1 to 40 carbon atoms or can bea polymeric group, for example having a molecular weight of 500 to50,000. The groups R¹, R², R³, R⁴ could contain as substituents a totalof at least two or more alcoholic hydroxyl groups.

In certain embodiments, the amidine of the metal amidine complex isN′-cyclohexyl-N,N-dimethylformamidine,N′-methyl-N,N-di-n-butylacetamidine,N′-octadecyl-N,N-dimethylformamidine,N′-cyclohexyl-N,N-dimethylvaleramidine,1-methyl-2-cyclohexyliminopyrrolidine,3-butyl-3,4,5,6-tetrahydropyrimidine, N-(hexyliminomethyl)morpholine,N-(α-(decylimino ethyl)ethyl)pyrrolidine,N′-decyl-N,N-dimethylformamidine, N′-dodecyl-N,N-dimethylformamidine,N′-cyclohexyl-N,N-acetamidine, pentamethylguanidine,tetramethylguanidine, or heptamethylisobiguanide.

In certain embodiments, the amidine of the metal amidine complex is anamidine in which one of the pairs R²-R³ or R²-R⁴ forms a 5 to 7 memberedring consisting of the two amidine nitrogen atoms and one of the pairsR¹-R³ or R¹-R⁴ forms a 5 to 9 membered ring consisting of one amidinenitrogen atom and carbon atoms. In specific embodiments, the amidine is1,5-diazabicyclo(4.3.0) none-5-ene, 1,8-diazabicyclo(5.4.0) undec-7-ene,1,4-diazabicyclo(3.3.0)oct-4-ene, 2-methyl-1,5-diazabicyclo(4.3.0)none-5-ene, 2,7,8-trimethyl-1,5-diazabicyclo(4.3.0) none-5-ene,2-butyl-1,5-diazabicyclo(4.3.0) none-5-ene or 1,9-diazabicyclo(6.5.0)tridec-8-ene.

Particular amidine groups are those in which the groups R² and R³ arejoined to form with the linking —N═C—N— a heterocyclic ring, for examplean imidazoline, imidazole, tetrahydropyrimidine, dihydropyrimidine orpyrimidine ring. Acyclic amidines and guanidines can alternatively beused.

In other embodiments, the amidine of the metal amidine complex is anamidine of the following formula:

where R⁵, R⁶, R⁷, and R⁸ are independently represent hydrogen, alkyl, orsubstituted alkyl, hydroxyalkyl, aryl, aralkyl, cycloalkyl,heterocyclics, ether, thioether, halogen, —N(R)₂, polyethylenepolyamines, nitro groups, keto groups, ester groups, or carbonamidegroups, alkyl substituted with the various functional groups describedabove. In other embodiments, the amidine of the metal amidine complex isnot an amidine of the aforementioned formula.

In certain embodiments, the amidine of the metal amidine complex isN-(2-Hydroxyethyl)imidazole, N-(3-Aminopropyl)imidazole,4-(hydroxymethyl) Imidazole, 1-(tert-butoxycarbonyl)imidazole,Imidazole-4-propionic acid, 4-carboxyimidazole, 1-butylimidazole,2-methyl-4-imidazolecarboxylic acid, 4-formyl imidazole,1-(ethoxycarbonyl)imidazole, reaction product of propylene oxide withimidazole and 2-methyl imidazole, 1-trimethylsilyl imidazole,4-(hydroxymethyl) Imidazole hydrochloride, copolymer of1-chloro-2,3-epoxypropane and imidazole, 1(p-toluenesulfonyl)imidazole,1,1′-carbonylbisimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole,2-phenyl-2-imidazoline pyromellitate, 4-(hydroxymethyl) Imidazolepicrate, reaction product of 2-propenoic acid with4,5-dihydro-2-nonyl-1H-imidazole-1-ethanol and2-heptyl-4,5-dihydro-1H-imidazole-1-ethanol, disodium salts,1-(cyanoethyl)-2-undecylimidazole trimellitate,1-(2-hydroxypropyl)imidazole formate, sodium imidazolate, or silverimidazolate.

In certain embodiments, the amidine of the metal amidine complex is acyclic amidine imidazoline or tetrahydropyrimidine of the formula:

in which n=2 or 3, m=1 or 2, R⁹, R¹⁰ and R¹¹ are identical or different,and represent hydrogen, alkyl, or substituted alkyl, hydroxyalkyl, aryl,aralkyl, cycloalkyl, heterocyclics, ether, thioether, halogen, —N(R)₂,polyethylene polyamines, nitro groups, keto groups, ester groups, orcarbonamide groups, alkyl substituted with the various functional groupsdescribed above, and R represents alkyl, alkylene, an aryl, aralkyl,cycloalkyl or heterocyclic radical, substituted if desired with halogen,nitro groups, alkyl groups, alkoxy groups or amino groups, and, whenm=1, represents also hydrogen, a plurality of radicals being able to bejoined, also by hetero atoms such as O, N or S, if desired. Salts of theabove structures include carboxylic (aliphatic, aromatic and polycarboxylic), carbonic, sulfonic and phosphoric acid salts. In certainembodiments, the amidine of the metal amidine complex is not an amidineof the aforementioned formula.

In other embodiments, R⁹, R¹⁰, R¹¹ are independently hydrogen, alkyl,alkenyl or alkoxy of 1 to 36 carbons, cycloalkyl of 6 to 32 carbons oralkylamino of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms,phenyl, hydroxyalkyl or hydroxycycloalkyl of 1 to 20 carbon atoms,methoxyalkyl of 1 to 20 carbon atoms, aralkyl of 7 to 9 carbon atoms,said aralkyl wherein the aryl group is further substituted by alkyl of 1to 36 carbon atoms.

When m=2, R is alkylene of 1 to 12 carbons or arylene of 6 to 10carbons, or a plurality of radicals being able to be joined, containinghetero atoms also by hetero atoms such as O, N or S, if desired.

In some embodiments imidazoline structures are where R is a long chainalkyl up to 18 carbon atoms, m=1 and R¹¹ is one of 2-hydroxyethyl, or2-aminoethyl or 2-amido ethyl substituents.

In certain embodiments, the amidine of the metal amidine complex is1H-Imidazole-1-ethanol, 2-(8Z)-8-heptadecenyl-4,5-dihydro,1H-Imidazole-1-ethanol, 2-(8Z)-8-heptadecenyl-4,5-dihydro, monoacetatesalt, 1H-Imidazole-1-ethanol, -4,5-dihydro,-2-(9Z)-9-octadecenyl,1H-Imidazole, 4,5-dihydro,-2-(9Z)-9-octadecenyl, oleyl hydroxyethylimidazoline, 1H-Imidazole-1-ethanol, 4,5-dihydro-2-undecyl-,1H-Imidazole-1-ethanol, 2(-8-heptadecenyl)-4,5-dihydro,1-(2-hydroxyethyl)-2-tall oil alkyl-2-imidazoline, azelaic acid salt,1H-Imidazole-1-ethanol, 2-heptadecyl-4,5-dihydro,1H-Imidazole-1-ethanol, 2-nonyl-4,5-dihydro, 1H-Imidazole-1-ethanol,4,5-dihydro-2-C₁₅₋₁₇-unsaturated alkyl derivatives,1H-Imidazole-1-ethanol, 4,5-dihydro-2-norcoco alkyl derivatives,1H-Imidazole-1-ethanol, 4,5-dihydro-2-nortall-oil alkyl derivatives,reaction product of 4,5-dihydro-2-nonyl 1H-Imidazole-1-ethanol, and4,5-dihydro-2-heptyl 1H-Imidazole-1-ethanol with 2-propenoic acid,1-propane sulfonic acid, 3-chloro-2-hydroxy-mono sodium salt reactionproducts with 2-(8Z)-8-heptadecenyl-4,5-dihydro 1H-Imidazole-1-ethanol,chloroacetic acid sodium salt reaction products with1H-Imidazole-1-ethanol, 4,5-dihydro-2-norcoco alkyl derivatives, andsodium hydroxide, 2-(8-heptadecenyl)-4,5-dihydro1H-Imidazole-1-ethanamine, or the 9-octadecenoic acid compound with2-(8-heptadecenyl)-4,5-dihydro 1H-Imidazole-1-ethanamine.

Unless otherwise noted, an “alkyl having up to 30 carbon atoms,” as usedherein, refers to a branched or unbranched radical such as, for example,methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl,tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, I,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl,decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,eicosyl or docosyl.

Unless otherwise noted, an “alkyl having 2 to 25 carbon atoms which isinterrupted by oxygen or sulfur,” or an “alkyl having 3 to 25 carbonatoms which is interrupted by oxygen or sulfur,” refers to an alkyl orthe specified number of carbon atoms which can be interrupted one ormore times, for example, CH₃—O—CH₂—, CH₃—S—CH₂—, CH₃—O—CH₂CH₂—O—CH₂—,CH₃—(O—CH₂CH₂—)₂O—CH₂—, CH₃—(O—CH₂CH₂—)₃O—CH₂— orCH₃—(O—CH₂CH₂—)₄O—CH₂—.

Unless otherwise noted, an “alkenyl having 2 to 24 carbon atoms,” asused herein, refers to a branched or unbranched radical, for example,vinyl, propenyl, 2-butenyl, 3-butenyl isobutenyl, n-2,4pentadienyl,3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, isododecenyl, oleyl,n-2-octadecenyl or n-4-octadecenyl. C₄-C₁₅ Cycloalkyl, or C₅-C₁₅cycloalkyl, which is unsubstituted or substituted.

C₅-C₁₅ Cycloalkenyl which is unsubstituted or substituted by C₁-C₄ alkyland/or carboxyl and which may contain 1 to 3 branched or unbranchedalkyl group radicals and/or 1 or 2 carboxyl groups, can be, for example,cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl,2-carboxycyclohexyl, 3-carboxycyclohexyl, methylcyclohexyl,dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl,cycloheptyl, cyclooctyl or cyclododecyl.

C₅-C₁₅ Cycloalkenyl which is unsubstituted or substituted by C₁-C₄ alkyland/or carboxyl and which may contains 1 to 3 branched or unbranchedalkyl group radicals and/or 1 or 2 carboxyl groups, can be, for example,cyclopentenyl, methylcyclopentenyl, dimethylcyclopentenyl, cyclohexenyl,2-carboxycyclohexenyl, 3-carboxycyclohexenyl,2-carboxy-4-methylcyclohexenyl, methylcyclohexenyl,dirnethylcyclohexenyl, trimethylcyclohexenyl, tert-butylcyclohexenyl,cycloheptenyl, cyclooctenyl or cyclododecenyl, e.g., C₅-C₁₂cycloalkenyl, in particular C₅-C₁₈ cycloalkenyl, e.g., cyclohexenyl.

C₁₃-C₂₆ polycycloalkyl can be, for example, the C₁₃-C₂₆ polycycloalkyls,which occur in naphthenic acid [J. Buckingham, Dictionary of OrganicCompounds, Vol. 4, page 4152, 5th Edition (1982)].

C₇-C₉ Phenylalkyl which is unsubstituted or substituted on the phenylradical by C₁-C₄ alkyl and which may contain 1 to 3 branched orunbranched alkyl group radicals can be, for example, benzyl,α-methylbenzyl, α,α-dimethylbenzyl 2-phenylethyl, 2-methylbenzyl,3-methylbenzyl, 4methylbenzyl, 2,4-dimethylbenzyl, 2,6-dimethylbenzyl or4-tert-butylbenzyl, e.g., benzyl.

A 5- or 6-membered heterocyclic ring which is unsubstituted orsubstituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen or carboxyl and whichmay contain 1 to 3, branched or unbranched alkyl or alkoxy groupradicals, and 1 to 3 heteroatoms from the group consisting of nitrogen,oxygen and sulfur can be, for example, thienyl, 2-methylthienyl,3-chlorothienyl, 3-methoxythienyl, tetrahydrofuranyl, furyl,pyrrolidinyl, 1-methylpyrrolidinyl, pyrrolyl, thiazolyl, isothiazolyl,imidazolyl, carboxyimidazolyl, triazolyl, tetrazolyl, oxazolyl,isoxazolyl, pyridyl, piperidinyl, morpholinyl, pyrazinyl,carboxypyrazinyl, piperazinyl, triazinyl or 2,6-dimethoxytriazonyl.

A 5- or 6-membered heterocyclic ring which is unsubstituted orsubstituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen or carboxy and isbenzo-fused, which may contain 1 to 3 branched or unbranched alkyl oralkoxy group radicals and 1 to 3 heteroatoms from the group consistingof nitrogen, oxygen and sulfur can be, for example, benzothiazolyl,5-chlorobenzothiazolyl, 5-methoxybenzothiazolyl, 5-methylbenzothiazolyl,benzoimidazolyl, benzooxazolyl, benzoisothiazolyl or benzothienyl.

Unless otherwise noted, an “alkoxy having up to 18 carbon atoms,” asused herein, refers to a branched or unbranched radical such as, forexample, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy,pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, tetradecyloxy,hexadecyloxy or octadecyloxy. C₂-C₁₈ Alkoxy which is interrupted byoxygen or sulfur can be, for example, CH₃—O—CH₂CH₂O—, CH₃—S—CH₂CH₂O—,CH₃—O—CH₂CH₂—O—CH₂CH₂O—, CH₃—S—CH₂CH₂—S—CH₂CH₂O—,CH₃—S—CH₂CH₂—O—CH₂CH₂O—CH₃—(O—CH₂CH₂—)₂O—CH₂CH₂O—,CH₃—(O—CH₂CH₂—)₃O—CH₂CH₂O— or CH₃—(O—CH₂CH₂—)₄O—CH₂CH₂—.

Phenyl or naphthyl substituted by C₁-C₄ alkyl, which preferably contains1 to 3 alkyl groups, can be, for example, o-, m- or p-methylphenyl2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl,2,6-dimethylphenyl, 3,4dimethylphenyl, 3,5-dimethylphenyl,2-methyl-6-ethylphenyl, 4tert-butylphenyl, 2-ethylphenyl,2,6-diethylphenyl, 1-methylnaphthyl, 2-methylnaphthyl, 4-methylnaphthyl,1,6-dimethylnaphthyl or 4-tert-butylnaphthyl.

C₁₀-C₁₂ Naphthylalkyl which is unsubstituted or substituted on thenaphthyl ring system by C₁-C₄ alkyl and which may contain 1 to 3branched or unbranched alkyl group radicals can be, for example,naphthylmethyl, α-methylnaphthylmethyl, α,α-dimethylnaphthylmethyl,naphthylethyl, 2-methyl-1-naphthylmethyl, 3-methyl-1-naphthylmethyl,4-methyl-1-naphthylmethyl, 2,4-dimethyl-1-naphthylmethyl,2,6-dimethyl-1-naphthylmethyl or 4-tert-butyl-1-naphthylmethyl.

An unsubstituted or C₁-C₄ alkyl-substituted C₅-C₁₂ cycloalkylidene ringwhich may contain 1 to 3 branched or unbranched alkyl group radicals canbe, for example, cyclopentylidene, methylcyclopentylidene,dimethylcyclopentylidene, cyclohexylidene, methylcyclohexylidene,dimethylcyclohexylidene, trimethylcyclohexylidene,tert-butylcyclohexylidene, cycloheptylidene, cyclooctylidene,cyclodecylidene or cyclododecylidene, e.g., cyclohexylidene andtert-butylcyclohexylidene.

Unless otherwise noted, a “halogen,” as used herein, refers to chlorine,bromine or iodine, for example, chlorine.

Unless otherwise noted, a “haloalkyl having up to 25 carbon atoms,” asused herein, refers to a branched or unbranched radical such as, forexample, chloromethyl, chloroethyl, chloropropyl, chlorobutyl or3-chloro-1-butyl.

Unless otherwise noted, an “alkylthio having up to 18 carbon atoms,” asused herein, refers to a branched or unbranched radical such as, forexample, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio,isobutylthio, pentylthio, isopentylthio, hexylthio, heptylthio,octylthio, decylthio, tetradecylthio, hexadecylthio or octadecylthio.

C₁-C₄ Alkyl-substituted phenoxy or naphthoxy, which preferably contains1 to 3 alkyl groups, can be for example o-, m- or p-methylphenoxy,2,3-dimethylphenoxy, 2,4dimethylphenoxy, 2,5-dimethylphenoxy,2,6-dimethylphenoxy, 3,4dimethylphenoxy, 3,5-dimethylphenoxy,2-methyl-6-ethylphenoxy, 4-tert-butylphenoxy, 2-ethylphenoxy,2,6-diethylphenoxy, 1-methylnaphthoxy, 2-methylnaphthoxy,4-methylnaphthoxy, 1,6-dimethylnaphthoxy or 4-tert-butylnaphthoxy.

C₇-C₉ Phenylalkoxy which is unsubstituted or substituted on the phenylring by C₁-C₄ alkyl, and may contain 1 to 3 branched or unbranched allylgroup radicals, can be for example benzyloxy, 2-phenylethoxy,2-methylbenzyloxy, 3-methylbenzyloxy, 4-methylbenzyloxy,2,4-dimethylbenzyloxy, 2,6-dimethylbenzyloxy or 4-tert-butylbenzyloxy.Benzyloxy is preferred.

C₁₀-C₁₂ Naphthylalkoxy which is unsubstituted or substituted on thenaphthyl ring system by C₁-C₄ alkyl, and preferably contains 1 to 3branched or unbranched alkyl group radicals, can be for examplenaphthylmethoxy, naphthylethoxy, 2-methyl-1-naphthylmethoxy,3-methyl-1-naphthylmethoxy, 4-methyl-1-naphthylmethoxy,2,4-dimethyl-1-naphthylmethoxy, 2,6-dimethyl-1-naphthylmethoxy or4-tert-butyl-1-naphthylmethoxy.

Unless otherwise noted, a “C₁-C₁₈ alkylene,” as used herein, refers to abranched or unbranched radical such as, for example, methylene,ethylene, propylene, tetramethylene, pentamethylene, hexamethylene,heptamethylene, octamethylene, decamethylene, dodecamethylene oroctadecamethylene.

Unless otherwise noted, a “C₂-C₁₈ alkylene which is interrupted byoxygen or sulfur,” as used herein, refers to a C₂-C₁₈ alkylene which canbe interrupted one or more times, for example —CH₂—O—CH₂—, —CH₂—S—CH₂—,—CH₂—NH—CH₂—, —CH₂—O—CH₂CH₂—O—CH₂—, —CH₂—(O—CH₂CH₂—)₂O—CH₂—,—CH₂—(O—CH₂CH₂—)₃O—CH₂—, —CH₂—(O—CH₂CH₂—)₄O—CH₂— or —CH₂CH₂—S—CH₂CH₂—.

Unless otherwise noted, a “C₄-C₁₈ alkylene interrupted by oxygen,sulfur, or an optionally alkyl-substituted nitrogen,” as used herein,refers to a C₄-C₁₈ alkylene, which can be interrupted one or more times,for example —CH₂CH₂—NH—CH₂CH₂—, —CH₂CH₂—N(CH₃)—CH₂CH₂—,—CH₂CH₂—NH—CH₂CH₂CH₂—, —CH₂CH₂—S—CH₂CH₂—, —CH₂CH₂—O—CH₂CH₂—O—CH₂CH₂—,—CH₂CH₂NH—CH₂CH₂—NH—CH₂CH₂CH₂—, —CH₂CH₂—(O—CH₂CH₂—)₂O—CH₂CH₂—,—CH₂CH₂—(O—CH₂CH₂—)₃O—CH₂CH₂— or —CH₂CH₂—(O—CH₂CH₂—)₄O—CH₂CH₂—.

C₂-C₁₈ alkenylene can be, for example vinylene, methylvinylene,octenylethylene or dodecenylethylene. C₂-C₁₂ Alkenylene is preferred,especially C₂-C₈ alkenylene. C₂-C₁₈ alkenylene can be forexample—2-propynylene 2-butynylene 2-pentynylene, 2-hexynylene,3-hexynylene, 3-heptynylene, 2-decynylene, 4-decynylene or 8-Alkylidenehaving 2 to 20 carbon atoms can be for example ethylidene, propylidene,butylidene, pentylidene, 4-methylpentylidene, heptylidene, nonylidene,tridecylidene, nonadecylidene, 1-methylethylidene, 1-ethylpropylidene or1-ethylpentylidene.

Phenylallidene having 7 to 20 carbon atoms can be for examplebenzylidene, 2-phenylethylidene or 1-phenyl-2-hexylidene.

Unless otherwise indicated, a “C₅-C₉ cycloalkylene,” as used herein,refers to a saturated hydrocarbon group having two free valences and atleast one ring unit and can be, for example, cyclopentylene,cyclohexylene, cycloheptylene or cyclooctylene. Cyclohexylene ispreferred.

An Unsubstituted or C₁-C₄ alkyl-substituted phenylene or naphthylene canbe, for example, 1,2-, 1,3-, or 1,4-phenylene; or 1,2-, 1,3-, 1,4-,1,6-, 1,7-, 2,6-, or 2,7-naphthylene, e.g., phenylene.

In certain embodiments, the metal amidine complexes described herein areprepared by heating 1 mole of metal carbon/late with 4 moles of amidinein methanol. The mixture is held at about 50° C. for about 2 hours oruntil it becomes a clear solution. The clear solution is filtered anddried. In some embodiments, the dried catalyst is then optionallyblended with fumed silica. A suitable fumed silica is SIPERNAT 50S fromDegussa Corporation.

A variety of main chain skeleton are useful in the organic polymer(s)used in the present disclosure, which have an active silicon group.

Specific examples thereof include polyoxyalkylene polymers such aspolyoxyethylene, polyoxypropylene, polyoxybutylene,polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer,polyoxypropylene-polyoxybutylene copolymer and the like; hydrocarbonpolymers such as ethylene-propylene copolymer, polyisobutylene,copolymer made from isobutylene and isoprene or the like,polychloroprene, polyisoprene, copolymer made from isoprene orbutadiene, acrylonitrile, and/or styrene or the like, polybutadiene,copolymer made from isoprene or butadiene, acrylonitrile, and styrene orthe like, hydrogenated polyolefin polymers obtained by hydrogenatingthese polyolefin polymers, and other hydrocarbon polymers; polyesterpolymers each obtained by condensing a dibasic acid such as adipic acidand glycol, or by ring-opening-polymerizing a lactone; (meth)acrylicacid ester polymers each obtained by radical-polymerizing ethyl(meth)acrylate, butyl (meth)acrylate, or some other monomer; vinylpolymers each obtained by radical-polymerizing a (meth)acrylic acidester monomer, vinyl acetate, acrylonitrile, styrene or some othermonomer; graft polymers each obtained by polymerizing the vinyl monomerin any one of the above-mentioned organic polymers; polysulfidepolymers; polyamide 6 obtained by ring-opening-polymerizingε-caprolactam, polyamide 6,6 obtained by polycondensinghexamethylenediamine and adipic acid, polyamide 6,10 obtained bypolycondensing hexamethylenediamine and sebacic acid, polyamide 11obtained by polycondensing ε-aminoundecanoic acid, polyamide 12 obtainedby ring-opening-polymerizing ε-aminolaurolactam, copolymer polyamideseach having two or more components out of the above-mentionedpolyamides, and other polyamide polymers; a polycarbonate polymerproduced by polycondensing bisphenol A and carbonyl chloride; diallylphthalate polymers; and other organic polymers. More preferred aresaturated hydrocarbon polymers such as polyisobutylene, hydrogenatedpolyisoprene and hydrogenated polybutadiene, the polyoxyalkylenepolymers, and the (meth)acrylic acid ester polymers since they have arelatively low glass transition temperature and give a cured productexcellent in cold resistance.

The glass transition temperature of the polymer(s) of the component (A)is not particularly limited, and is generally 20° C. or lower, e.g., 0°C. or lower, e.g., −20° C. or lower. If the glass transition temperatureis higher than 20° C., the viscosity becomes high in winter or in colddistricts so that the workability may deteriorate. Moreover, theflexibility of the cured product falls so that the elongation may lower.The glass transition temperature can be obtained by DSC measurement.

The polyoxyalkylene polymers and (meth)acrylic acid ester polymers areparticularly preferred since they have high moisture permeability andcan give a one-part type composition excellent in depth curability andadhesiveness. The polyoxyalkylene polymers are most preferred.

The reactive silicon group contained in thereactive-silicon-group-containing organic polymer(s) is a group whichhas a hydroxyl group or hydrolyzable group bonded to a silicon atom andwhich can form a siloxane bond by reaction accelerated by a silanolcondensing catalyst so as to be crosslinked. The reactive silicon groupmay be a group represented by the following general formula (2):—(SiR¹ _(2-a)X_(a)O)_(m)—SiR³ _(3-b)X_(b)  (2)wherein R¹ and R³ each independently represent a substituted orunsubstituted hydrocarbon group having 1 to 20 carbon atoms, or atriorganosiloxy group represented by (R′)₃SiO— wherein R′s are eachindependently a substituted or unsubstituted hydrocarbon group having 1to 20 carbon atoms, R′s, the number of which is three, may be the sameor different), Xs each independently represent a hydroxyl or ahydrolyzable group, a is 0, 1 or 2, b is 0, 1, 2 or 3 provided that aand b are not both 0 and m is 0 or an integer of 1 to 19.

The hydrolyzable group is not particularly limited, and may be ahydrolyzable group known in the prior art. Specific examples thereofinclude a hydrogen atom, halogen atoms, and alkoxy, acyloxy, ketoximate,amino, amide, acidamide, aminooxy, mercapto, alkenyloxy groups and thelike, for example, alkoxy, acyloxy, ketoxymate, amino, amide, aminooxy,mercapto and alkenyloxy groups, and in many embodiments alkoxy groups asthe groups have mild hydrolyzability and good handleability.

One to three hydrolyzable groups or hydroxyl groups which are each thesame as described above can be bonded onto the single silicon atom. Thevalue of (a+b) is preferably from 1 to 5. When the hydrolyzable groupsor hydroxyl groups the number of which is two or more are bonded intothe reactive silicon group, they may be the same or different.

One or more silicon atoms are contained in the reactive silicon group inorder to form the group. The number of the silicon atoms is preferably20 or less in the case of silicon atoms linked to each other through oneor more siloxane bonds or the like.

In particular, a reactive silicon group represented by the followinggeneral formula (3) is preferred since the group is easily available:—SiR³ _(3-c)X_(c)  (3)(wherein R³ and X have the same meanings as described above, and c is 1,2, or 3).

Specific examples of R¹ and R² include alkyl groups such as a methyl,ethyl group and the like; cycloalkyl groups such as a cyclohexyl groupand the like; aryl groups such as a phenyl group and the like; aralkylgroups such as a benzyl group and the like; and triorganosiloxy groupsrepresented by (R′)₃SiO— wherein R′s are each a methyl, phenyl group, orthe like. Among them, a methyl and ethyl groups are particularlypreferred.

More specific examples of the reactive silicon group includetrimethoxysilyl, triethoxysilyl, triisopropoxysilyl,dimethoxymethylsilyl, diethoxymethylsilyl, and diisopropoxymethylsilylgroups. More preferred are the trimethoxysilyl, triethoxysilyl anddimethoxymethylsilyl group, and particularly preferred is thetrimethoxysilyl group since they have a high activity to give a goodcurability. From the viewpoint of storage stability, thedimethoxymethylsilyl group is particularly preferred. The triethoxysilylgroup is particularly preferred since ethanol generated during thehydrolysis reaction of the reactive silicon group is more innocuous,than methanol generated from the trimethoxysilyl group.

It is essential that the curable composition of the present disclosurecontains an organic polymer having, as the reactive-silicon-containinggroup in at least one portion thereof, a group represented by thefollowing general formula (1):—(CR² ₂)₂—(SiR¹ _(2-a)X_(a)O)_(m)—SiX₃  (1)(wherein R¹, X, a and m have the same meanings as described above, andR² are each independently a hydrogen atom, or a substituted orunsubstituted hydrocarbon group having 1 to 10 carbon atoms).

The organic polymer having a reactive silicon group having threehydrolyzable groups on a silicon atom tends to give a curablecomposition having good restorability, endurance, and creep resistance.

The ratio of the organic polymer(s) having a group represented by thegeneral formula (1) in all of the organic polymer(s) (A) used in thepresent disclosure will vary, and is preferably 10% or more by weight,more preferably 20% or more by weight in order to yield a curablecomposition wherein speedy curability and storage stability aresatisfied.

The reactive silicon group may be introduced by a known method.Specifically, the following methods can be exemplified:

(A) An organic polymer having in the molecule thereof a functional groupsuch as a hydroxyl group is caused to react with an organic compoundhaving an active group reactive with this functional group and anunsaturated group to yield an organic polymer having the unsaturatedgroup. Alternatively, the polymer is copolymerized with anunsaturated-group-containing epoxy compound, thereby yielding anunsaturated-group-containing polymer. The resultant reaction product isthen hydrosilated, using a hydrosilane.(B) An unsaturated-group-containing organic polymer obtained in the samemanner as in the method (A) is caused to react with a compound having amercapto group and a reactive silicon group.(C) An organic polymer having in the molecule thereof a functional groupsuch as a hydroxyl group, epoxy group or isocyanate group is caused toreact with a compound having a functional group reactive with thisfunctional group and a reactive silicon group.

Out of the above-mentioned methods, the method (A) and the method ofcausing a polymer having a hydroxyl group at its terminal to react witha compound having an isocyanate group and a reactive silicon group amongvariations of the method (C) are preferred since a high conversion ratiocan be obtained in a relatively short reaction time. The method (A) isparticularly preferred since the reactive-silicon-group-containingorganic polymer obtained by the method (A) becomes a curable compositionhaving a lower viscosity and a better workability than the organicpolymer obtained by the method (C) and the organic polymer obtained bythe method (B) generates a strong odor based on mercaptosilane.

Specific examples of the hydrosilane used in the method (A) includehalogenated silanes such as trichlorosilane, methyldichlorosilane,dimethylchlorosilane, and phenyldichlorosilane; alkoxysilanes such astrimethoxysilane, triethoxysilane, methyldiethoxysilane,methyldimethoxysilane, and phenyldimethoxysilane; acyloxysilanes such asmethyldiacetoxysilane, and phenyldiacetoxysilane; and ketoximatesilanesuch as bis(dimethylketoximate)methylsilane,bis(cyclohexylketoximate)methylsilane and the like. However, thehydrosilane is not limited thereto. Among them, halogenated silanes, andalkoxysilanes are preferred, and alkoxysilanes are most preferred sincethey give a curable composition having good storage stability. Out ofthe alkoxysilanes, methyldimethoxysilane is particularly preferred sinceit is easily available and a curable composition containing the organicpolymer obtained therefrom has high curability, storage stability,elongation property and tensile strength.

Out of the above-mentioned hydrosilanes, a hydrosilane represented bythe following general formula (4) is preferred since a curablecomposition made of the organic polymer obtained by addition reaction ofthe hydrosilane compound has very good curability:H—SiX₃  (4)(wherein X has the same meaning as described above). Out of hydrosilanecompounds represented by the general formula (4), more preferred aretrialkoxysilanes such as trimethoxysilane, triethoxysilane,triisopropoxysilane and the like.

Out of the trialkoxysilanes, a trialkoxysilane having an alkoxy grouphaving one carbon atom (a methoxy group), such as trimethoxysilane andthe like, may accelerate disproportionation reaction, leading to adimethoxysilane. From the viewpoint of safe handling, it is preferableto use a trialkoxysilane having an alkoxy group having 2 or more carbonatoms and represented by the following general formula (5):H—Si(OR⁴)₃  (5)(wherein R⁴, are each independently an organic group having 2 to 20carbon atoms). Triethoxysilane is most preferred from the viewpoint ofavailability and safe handling.

The synthesis method (B) may be, for example, a method of introducing acompound having a mercapto group and a reactive silicon group into anunsaturated bond moiety of the organic polymer by radical additionreaction in the presence of a radical initiator and/or aradical-generating source. However, the method (B) is not particularlylimited. Specific examples of the compound having a mercapto group and areactive silicon group include γ-mercaptopropyltrimethoxysilane,γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane,γ-mercaptopropylmethyldiethoxysilane and the like.

Out of variations of the synthesis method (C), the method of causing apolymer having a hydroxyl group at its terminal to react with a compoundhaving an isocyanate group and a reactive silicon group may be, forexample, a method disclosed in JP-A-3-47825. However, the method is notparticularly limited. Specific examples of the compound having anisocyanate group and a reactive silicon group include γ-isocyanatepropyltrimethoxysilane, γ-isocyanate propylmethyldimethoxysilane,γ-isocyanate propyltriethoxysilane, γ-isocyanate propyldiethoxysilaneand the like.

The organic polymer(s) having a reactive silicon group may be linear orbranched with a number-average molecular weight thereof, from about 500to 100,000, more preferably from 1,000 to 50,000, in particularpreferably from 3,000 to 30,000. If the number-average molecular weightis less than 500, the elongation properties of the cured elastomer isinferior and if the molecular weight is more than 100,000 the curedproduct has an unacceptably high viscosity.

In order to obtain a rubber-like cured product exhibiting a highstrength, a high elongation and a low elasticity, the number of reactivesilicon groups contained in the organic polymer or each of the polymersis, on average, at least one, preferably from 1.1 to 5 per molecule ofthe polymer. If the number of the reactive silicon groups contained permolecule is less than one on average, the cure is insufficient and agood rubber-like elasticity behavior is not easily attained. Thereactive silicon groups may be present on a terminal of the main chainof the molecule chain of the organic polymer(s) or a terminal of a sidechain thereof, or may be present on both of the terminals. Inparticular, when the reactive silicon groups are present only on aterminal of the main chain of the molecular chain, a rubber-like curedproduct exhibiting a high strength, a high elongation and a lowelasticity is easily obtained since the effective network length of theorganic polymer component(s) contained in the cured product, which isfinally formed, becomes long.

The above-mentioned polyoxyalkylene polymers are each a polymer whichessentially has a recurring unit represented by the following generalformula (6):—R⁵—O—  (6)(wherein R⁵ is a linear or branched alkylene group having 1 to 14 carbonatoms). R⁵ in the general formula (6) is preferably a linear or branchedalkylene group having 1 to 14 carbon atoms, preferably 2 to 4 carbonatoms.

The main chain skeleton of the polyoxyalkylene polymer may be made ofonly one kind of recurring unit, or may be made of two or more kinds ofrecurring units. In the case that the composition is used, inparticular, for a sealant, a material made of a polymer made mainly of apropylene oxide polymer is preferred since the material is amorphous andhas a relatively low viscosity.

Examples of the method for synthesizing the polyoxyalkylene polymerinclude a polymerization method based on an alkali catalyst such as KOH,a polymerization method based on a transition metal compound/porphyrincomplex catalyst obtained by reaction between an organic aluminumcompound and porphyrin, as described in JP-A-61-215623, a polymerizationmethod based on a composite metal cyanide complex catalyst, as describedin JP-B-46-27250, JP-B-59-15336, and U.S. Pat. Nos. 3,278,457,3,278,458, 3,278,459, 3,427,256, 3,427,334, 3,427,335, and otherpublications; a polymerization method using a catalyst made of apolyphosphazene salt, as exemplified in JP-A-10-273512; and apolymerization method using a catalyst made of a phosphazene compound,as exemplified in JP-A-11-060722. However, the method is not limitedthereto.

Examples of the method for producing the polyoxyalkylene polymer havinga reactive silicon group include methods suggested in JP-B-45-36319 and46-12154, JP-A-50-156599, 54-6096, 55-13767, 55-13468 and 57-164123,JP-B-3-2450, and U.S. Pat. Nos. 3,632,557, 4,345,053, 4,366,307,4,960,844, and other publications; and polyoxyalkylene polymers having anumber-average molecular weight of 6,000 or more and a Mw/Mn of 1.6 orless, which has a high molecular weight and a narrow molecular weightdistribution, as suggested in JP-A-61-197631, 61-215622, 61-215623,61-218632, 3-72527, 3-47825, and 8-231707. However, the method is notparticularly limited thereto.

The above-mentioned polyoxyalkylene polymers having a reactive silicongroup may be used alone or in combination of two or more thereof.

The saturated hydrocarbon polymers are each a polymer which does notsubstantially contain any carbon-carbon unsaturated bond other thanthose in an aromatic ring. The polymer which constitutes the skeletonthereof can be obtained by a method (1) of polymerizing, as a mainmonomer, an olefin compound having 2 to 6 carbon atoms, such asethylene, propylene, 1-butene or isobutylene, a method (2) ofhomo-polymerizing a diene compound such as butadiene or isoprene, orcopolymerizing the diene compound and one or more out of theabove-mentioned olefin compounds, and then hydrogenating the homopolymeror copolymer, or some other methods. Isobutylene polymers orhydrogenated polybutadiene polymers are preferred since one or morefunctional groups can easily be introduced into a terminal thereof, themolecular weight thereof is easily controlled and further the number ofthe terminal functional groups can be made large. The isobutylenepolymers are particularly preferred.

The polymer having a main chain skeleton made of a saturated hydrocarbonpolymer has a very good characteristic in heat resistance, weatherresistance, endurance, and humidity blocking property.

The isobutylene polymers may each be a polymer wherein all of theirmonomer units are isobutylene units, or a copolymer made fromisobutylene units and a different monomer. From the viewpoint ofrubber-like characteristics, the recurring units originating fromisobutylene are contained preferably in an amount of 50% or more byweight, more preferably in an amount of 80% or more by weight, inparticular preferably in an amount of 90 to 99%.

As the method for synthesizing the saturated hydrocarbon polymer,hitherto various polymerization methods have been reported. In recentyears, in particular, a large number of, what is called, livingpolymerizations have been developed. In the case of a saturatedhydrocarbon polymer, in particular, an isobutylene polymer, thefollowing are known: the polymer can easily be produced by usinginiferter polymerization as disclosed by Kennedy et al. (J. P. Kennedyet al., J. Polymer Sci., Polymer Chem. Ed. 1997, vol. 15, 2843); thepolymer can be produced by polymerization, so as to have a molecularweight of about 500 to 100,000 and a molecular weight distribution of1.5 or less; and various functional groups can be introduced into aterminal of the molecule.

The method for synthesizing the saturated hydrocarbon polymer having areactive silicon group is described in, for example, JP-B-4-69659 and7-108928, JP-A-63-254149, 64-22904 and 1-197509, Japanese PatentOfficial Gazette Nos. 2539445 and 2873395, JP-A-7-53882, and otherpublications. However, the method is not particularly limited thereto.

The above-mentioned saturated hydrocarbon polymers having a reactivesilicon group may be used alone or in combination of two or morethereof.

The (meth)acrylic acid ester monomer which constitutes the main chain ofthe above-mentioned (meth)acrylic acid ester polymers is notparticularly limited, and various monomers can be used. Examples thereofinclude (meth)acrylic acid based monomers such as (meth)acrylic acid,methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate,isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl(meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate,n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl(meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate,phenyl (meth)acrylate, tolyl (meth)acrylate, benzyl (meth)acrylate,2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate,2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl(meth)acrylate, glycidyl (meth)acrylate,γ-(methacryloyloxypropyl)trimethoxysilane,γ-(methacryloyloxypropyl)dimethoxymethylsilane, an ethylene oxide adductof (meth)acrylic acid, trifluoromethylmethyl (meth)acrylate,2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl(meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate,perfluoroethyl (meth)acrylate, trifluoromethyl (meth)acrylate,bis(trifluoromethylmethyl) (meth)acrylate,2-trifluoromethyl-2-perfluoroethylethyl (meth)acrylate,2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl(meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate and the like.In the (meth)acrylic acid ester polymers, any (meth)acrylic acid estermonomer may be copolymerized with a vinyl monomer, which will bedescribed hereinafter. Examples of the vinyl monomer include styrenemonomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene,styrenesulfonic acid and salts thereof, and the like;fluorine-containing vinyl monomers such as perfluoroethylene,perfluoropropylene, fluorinated vinylidene and the like;silicon-containing vinyl monomers such as vinyltrimethoxysilane,vinyltriethoxysilane and the like; maleic anhydride, maleic acid, andmonoalkyl esters and dialkyl esters of maleic acid; fumaric acid,monoalkyl ester and dialkyl ester of fumaric acid; maleimide monomerssuch as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide,butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide,stearylmaleimide, phenylmaleimide, cyclohexylmaleimide and the like;nitrile-group-containing vinyl monomers such as acrylonitrile,methacrylonitrile and the like; amide-group-containing vinyl monomerssuch as acrylamide, methacrylamide and the like; vinyl esters such asvinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinylcinnamate and the like; alkenes such as ethylene, propylene and thelike; conjugated dienes such as butadiene, isoprene and the like; andvinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol andthe like. These may be used alone, or plural ones thereof may becopolymerized. Among them, a polymer made from a styrene monomer and a(meth)acrylic acid based monomer is preferred from the viewpoint ofphysical properties of the product, and others. More preferred is a(meth)acrylic polymer made from an acrylic acid ester monomer and amethacrylic acid ester monomer. Particularly preferred is an acrylicpolymer made from an acrylic acid ester monomer. In articles forordinary buildings, a butyl acrylate based monomer is further preferredsince the composition is required to have a low viscosity and the curedproduct is required to have a low modulus, a high elongation, weatherresistance, heat resistance and other physical properties. On the otherhand, in articles required to have oil resistance and others, for cars,a copolymer made mainly of ethyl acrylate is further preferred. Thispolymer made mainly of ethyl acrylate is excellent in oil resistance,but tends to be somewhat poor in low-temperature property (coldresistance); therefore, in order to improve the low-temperatureproperty, ethyl acrylate is partially substituted with butyl acrylate.However, a good oil resistance is gradually damaged with an increase inthe ratio of butyl acrylate. In articles required to have oilresistance, the ratio is preferably 40% or less, more preferably 30% orless. It is also preferred to use 2-methoxyethyl acrylate or2-ethoxyethyl acrylate, wherein oxygen is introduced into an alkyl groupof a side chain, in order to improve the low-temperature property andothers without damaging the oil resistance. However, when the alkoxygroup, which has an ether bond, is introduced to the side chain, a poorheat resistance tends to be exhibited; thus, when heat resistance isrequired, the ratio thereof is preferably 40% or less. The ratio isvaried, considering oil resistance, heat resistance, low-temperatureproperty and other physical properties necessary in accordance withusages or a requested purpose. In this way, an appropriate polymer canbe obtained. An unrestricted example excellent in physical balancesbetween oil resistance, heat resistance, low-temperature property andothers is a copolymer of ethyl acrylate/butyl acrylate/2-methoxyethylacrylate (ratio by weight: 40 to 50/20 to 30/30 to 20). In the presentdisclosure, a monomer out of these preferred monomers may becopolymerized with a different monomer, or may be block-copolymerizedthere with. At this time, the preferred monomer is contained preferablyat a ratio by weight of 40% or more. In the above-mentioned expressions,for example, (meth)acrylic acid represents acrylic acid and/ormethacrylic acid.

The method for synthesizing such a (meth)acrylic acid ester polymer isnot particularly limited, and may be a known method. However, thepolymer obtained by an ordinary free-radical polymerization method usingan azo compound, a peroxide or the like as a polymerization initiatorhas a problem that the value of the molecular weight distribution isgenerally as large as 2 or more, and the viscosity becomes high.Accordingly, it is preferred to use a living radical polymerizationmethod in order to yield a (meth)acrylic acid ester polymer having anarrow molecular weight distribution and a low viscosity and containing,at a terminal of the molecule chain thereof, a crosslinkable functionalgroup at a high content by percentage.

Out of variations of the “living radical polymerization method”, the“atom transfer radical polymerization method” of polymerizing the(meth)acrylic acid ester monomer, using an organic halide, halogenatedsulfonyl compounds or the like as an initiator and a transition metalcomplex as a catalyst, is more preferred as a method for producing a(meth)acrylic acid ester polymer having a specific functional groupsince the terminal has a halogen or the like, which is relativelyadvantageous for functional-group-converting reaction, and theflexibility in design of the initiator or the catalyst is large as wellas the characteristics of the above-mentioned “living polymerizationmethod” are exhibited. This atom transfer radical polymerization methodis described in, for example, Matyjaszewski et al., J. Am. Chem. Soc.,1995, vol. 117, 5614.

As the method for producing the (meth)acrylic acid ester polymer havinga reactive silicon group, a production process using a free radicalpolymerization method using a chain transfer agent is disclosed in, forexample, JP-B-3-14068 and 4-55444, and JP-A-6-211922. JP-A-9-272714 andothers disclose a production process using an atom transfer radicalpolymerization method. However, the method is not particularly limitedthereto.

The above-mentioned (meth)acrylic acid ester polymers having a reactivesilicon group may be used alone or in combination of two or morethereof.

These organic polymers having reactive silicon group may be used aloneor in combination of two or more thereof. Specifically, it is allowableto use an organic polymer obtained by blending two or more selected fromthe group consisting of the polyoxyalkylene polymers having a reactivesilicon group, the saturated hydrocarbon polymers having a reactivesilicon group, and the (meth)acrylic acid ester polymers having areactive silicon group.

The method for producing an organic polymer wherein a polyoxyalkylenepolymer having a reactive silicon group is blended with a (meth)acrylicacid ester polymer having a reactive silicon group is suggested inJP-A-59-122541, 63-112642, 6-172631 and 11-116763, and otherpublications. However, the method is not particularly limited thereto. Apreferred specific example thereof is a method of blending apolyoxyalkylene polymer having a reactive silicon group with a copolymerwhich has a reactive silicon group and has a molecular chain composedsubstantially of (meth)acrylic acid ester monomer units each having 1 to8 carbon atoms and represented by the following general formula (7)—CH₂—C(R⁶)(COOR⁷)  (7)(wherein R⁶ represents a hydrogen atom or a methyl group, and R⁷represents an alkyl group having 1 to 8 carbon atoms), and (meth)acrylicacid ester monomer units each having an alkyl group having 10 or morecarbon atoms and represented by the following general formula (8)—CH₂—C(R⁶)(COOR⁸)  (8)(wherein R⁶ has the same meaning as described above, and R⁸ representsan alkyl group having 10 or more carbon atoms).

Examples of R⁷ in the general formula (7) include alkyl groups having 1to 8 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to2 carbon atoms, such as a methyl, ethyl, propyl, n-butyl, t-butyl, and2-ethylhexyl group. The alkyl groups as R⁷ may be used alone or in theform of a mixture of two or more thereof.

Examples of R⁸ in the general formula (8) include long-chain alkylgroups having 10 or more carbon atoms, usually 10 to 30 carbon atoms,preferably 10 to 20 carbon atoms, such as lauryl, tridecyl, cetyl,stearyl, and behenyl groups. The alkyl groups as R.sup.8 may be usedalone or in the form of a mixture of two or more thereof in the samemanner as R⁷.

The molecular chain of the (meth)acrylic acid ester copolymer iscomposed substantially of the monomer units of the formula (7) and (8).The word “substantially” referred to herein means that the total amountof the monomer units of the formula (6) and (8) present in the copolymeris over 50% by weight. The total amount of the monomer units of theformula (7) and (8) is preferably 70% or more by weight.

The presence ratio by weight of the monomer units of the formula (7) tothe monomer units of the formula (8) is preferably from 95/5 to 40/60,more preferably from 90/10 to 60/40.

Examples of a monomer unit which is different from the monomer units ofthe formula (7) and (8) and may be contained in the copolymer includeacrylic acids such as acrylic acid, methacrylic acid and the like;monomers containing an amide group, such as N-methylolacrylamide,N-methylolmethacrylamide and the like, those containing an epoxy group,such as glycidyl acrylate, glycidyl methacrylate and the like, and thosecontaining a nitrogen-containing group, such as diethylaminoethylacrylate, diethylaminoethyl methacrylate and the like; and other monomerunits originating from acrylonitrile, styrene, α-methylstyrene, alkylvinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene,or the like.

An organic polymer wherein a saturated hydrocarbon polymer having areactive silicon group is blended with a (meth)acrylic acid estercopolymer having a reactive silicon group is suggested in JP-A-1-168764and 2000-186176, and other publications. However, the polymer is notlimited thereto.

A different example of the method for producing an organic polymercontaining, as a blend component, a (meth)acrylic acid ester copolymerhaving a reactive silicon functional group is a method of polymerizing a(meth)acrylic acid ester monomer in the presence of an organic polymerhaving a reactive silicon group. This production method is specificallydisclosed in JP-A-59-78223, 59-168014, 60-228516 and 60-228517, andother publications. However, the method is not limited thereto.

On the other hand, the main chain skeleton of the organic polymer(s) maycontain a different component such as a urethane bond component as longas the advantageous effects of the present disclosure are not largelydamaged.

The urethane bond component is not particularly limited, and an examplethereof is a group generated by reaction between an isocyanate group andan active hydrogen group (and the group may be referred to as an amidesegment hereinafter).

The amide segment is represented by the following general formula (9):—NR⁹—C(═O)—  (9)(wherein R⁹ represents a hydrogen atom or a substituted or unsubstitutedorganic group).

Specific examples of the amide segment include a urethane groupgenerated by reaction between an isocyanate group and a hydroxyl group;a urea group generated by reaction between an isocyanate group and anamino group; and a thiourethane group generated by reaction between anisocyanate group and a mercapto group, and the group. In the presentdisclosure, groups generated by causing the active hydrogen occurring inthe urethane group, the urea group and the thiourethane group to reactfurther with an isocyanate group are also contained in the category ofthe group of the formula (9).

An example of the method for producing a polymer having an amide segmentand a reactive silicon group with industrial ease is a method of causinga polymer having an active-hydrogen-containing group as its terminal toreact with an excessive amount of a polyisocyanate compound to prepare apolymer having an isocyanate group at its polyurethane main chainterminal, and subsequently or simultaneously causing a part or the wholeof individuals of the isocyanate group to react with a Z group of asilicon compound represented by the following general formula (10)Z—R¹⁰—SiR³ _(3-c)X_(c)  (10)(wherein R³, X and c have the same meanings as described above, and R¹⁰is a bivalent organic group, more preferably a substituted orunsubstituted bivalent hydrocarbon group having 1 to 20 carbon atoms;and Z is an active-hydrogen-containing group selected from hydroxyl,carboxyl, mercapto, and mono-substituted or unsubstituted amino groups),thereby producing the polymer. Examples of known organicpolymer-producing methods related to this production method includemethods disclosed in JP-B-46-12154 (U.S. Pat. No. 3,632,557),JP-A-58-109529 (U.S. Pat. No. 4,374,237), JP-A-62-13430 (U.S. Pat. No.4,645,816), JP-A-8-53528 (EP 0676403), JP-A-10-204144 (EP 0831108),JP-A-2003-508561 as Japanese Patent Application National Publication(U.S. Pat. No. 6,197,912), JP-A-6-211879 (U.S. Pat. No. 5,364,955),JP-A-10-53637 (U.S. Pat. No. 5,756,751), JP-A-11-100427, 2000-169544,2000-169545 and 2002-212415, Japanese Patent No. 3313360, U.S. Pat. Nos.4,067,844 and 3,711,445, and JP-A-2001-323040, and other publications.

Another example of the above-mentioned method is a method of reacting apolymer having an active-hydrogen-containing group at its terminal witha reactive-silicon-group-containing isocyanate compound represented bythe following general formula (11):O═C═N—R¹⁰—SiR³ _(3-c)X_(c)  (11)(wherein R³, R¹⁰, X and c have the same meanings as described above),thereby producing the polymer. Examples of known polymer-producingmethods related to this production method include methods disclosed inJP-A-11-279249 (U.S. Pat. No. 5,990,257), JP-A-2000-119365 (U.S. Pat.No. 6,046,270), JP-A-58-29818 (U.S. Pat. No. 4,345,053), JP-A-3-47825(U.S. Pat. No. 5,068,304), JP-A-11-60724, 2002-155145 and 2002-249538,WO 03/018658, WO 03/059981 and other publications.

Examples of the organic polymer have an active-hydrogen-containing groupat its terminal include oxyalkylene polymer having a hydroxyl group atits terminal (polyetherpolyol), polyacrylpolyol, polyesterpolyol,saturated hydrocarbon polymer having a hydroxyl group at its terminal(polyolefinpolyol), polythiol compounds, polyamine compounds,polyalkyleneimine and the like. Among them, polyesterpolyol,polyetherpolyol, polyacrylpolyol and polyolefinpolyol are preferredsince the resultant polymer has a relatively high glass transitiontemperature and the resultant cured product has very good coldresistance. The polyetherpolyol is particularly preferred since theresultant polymer has a low viscosity to exhibit a good workability andthe depth curability thereof is good. The polyacrylpolyol and thesaturated hydrocarbon polymers are more preferred since the curedproduct of the resultant polymer has good weather resistance and heatresistance.

As the polyetherpolyol, polyetherpolyol that is produced by any methodcan be used. Preferred is polyetherpolyol having, at its terminal, ahydroxyl group the number of individuals of which is at least 0.7 permolecular terminal on the average of all the molecules. Specificexamples thereof include oxyalkylene polymer produced by use of aconventional alkali metal catalyst; and oxyalkylene polymer produced bycausing an initiator such as a polyhydroxy compound, which has at leasttwo hydroxyl groups, to react with an alkylene oxide in the presence ofa composite metal cyanide complex or cesium.

Out of the above-mentioned polymerization methods, the polymerizationmethod using a composite metal cyanide complex is preferred since themethod makes it possible to yield oxyalkylene polymer having a lowerunsaturated degree, a narrow Mw/Mn, a lower viscosity, a high acidresistance and a high weather resistance.

The polyacrylpolyol may be a polyol having a skeleton of an alkyl(meth)acrylate (co)polymer and having in the molecule thereof a hydroxylgroup. The method for synthesizing the polymer is preferably a livingpolymerization method since a polymer having a narrow molecular weightdistribution and a low viscosity can be obtained. An atom transferradical polymerization method is more preferred. It is also preferred touse a polymer based on the so-called SGO process, which is obtained bysubjecting an alkyl acrylate ester monomer described in JP-A-2001-207157to continuous bulk polymerization at high temperature and high pressure.A specific example thereof is “UH-2000” manufactured by Toagosei Co.,Ltd.

Specific examples of the above-mentioned polyisocyanate compound includearomatic polyisocyanates such as toluene(tolylene)diisocyanate,diphenylmethane diisocyanate, xylylene diisocyanate and the like; andaliphatic polyisocyanates such as isophoronediisocyanate, andhexamethylenediisocyanate and the like.

The silicon compound of the general formula (10) is not particularlylimited, and specific examples thereof include amino-group-containingsilanes such as γ-aminopropyltrimethoxysilane,N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane,γ-(N-phenyl)aminopropyltrimethoxysilane,N-ethylaminoisobutyltrimethoxysilane and the like;hydroxy-group-containing silanes such as γ-hydroxypropyltrimethoxysilaneand the like; and mercapto-group-containing silanes such asγ-mercaptopropyltrimethoxysilane and the like, and the like. Asdescribed in JP-A-6-211879 (U.S. Pat. No. 5,364,955), JP-A-10-53637(U.S. Pat. No. 5,756,751), JP-A-10-204144 (EP 0831108), andJP-A-2000-169544 and 2000-169545, the following can also be used as thesilicon compound of the general formula (10): Michael addition reactantsmade from a variety of α,β-unsaturated carbonyl compounds and anamino-group-containing silane; and Michael addition reactants made froma variety of (meth)acryloyl-group-containing silanes and anamino-group-containing compound.

The reactive-silicon-group-containing isocyanate compound of the generalformula (11) is not particularly limited, and specific examples thereofinclude γ-trimethoxysilylpropylisocyanate,γ-triethoxysilylpropylisocyanate,γ-methyldimethoxysilylpropylisocyanate,γ-methyldiethoxysilylpropylisocyanate and the like. As described inJP-A-2000-119365 (U.S. Pat. No. 6,046,270), a compound obtained bycausing a silicon compound of the general formula (10) to react with anexcessive amount of the above-mentioned polyisocyanate compound can alsobe used as the reactive-silicon-group-containing isocyanate compound ofthe general formula (11).

When the amount of the amide segment in the main chain skeleton of theorganic polymer(s) which is/are the component (A) in the presentdisclosure is large, the viscosity of the organic polymer tends to behigh. After the storage of the polymer(s), the viscosity may also riseso that the workability of the resultant composition may lower.Accordingly, in order to obtain a composition having very good storagestability and workability, it is preferred that the amide segment is notsubstantially contained therein. On the other hand, the amide segment inthe main chain skeleton of the component (A) tends to cause animprovement in the curability of the composition of the presentdisclosure. Accordingly, when the main chain skeleton of thecomponent(s) (A) contains an amide segment, the number of individuals ofthe amide segment is preferably from 1 to 10, more preferably from 1.5to 5, in particular preferably from 2 to 3 per molecule on the average.If the number is less than 1, the curability may be sufficient. If thenumber is more than 10, the organic polymer becomes highly viscous sothat a composition poor in workability may be obtained.

A filler can be added to the composition of the present disclosure.Examples of the filler include reinforcing fillers such as fume silica,precipitating silica, crystalline silica, fused silica, dolomite,silicic anhydride, hydrated silicic acid, and carbon black and the like;ground calcium carbonate, colloidal calcium carbonate, magnesiumcarbonate, diatomaceous earth, calcined clay, clay, talc, titaniumoxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder,flint powder, zinc oxide, active zinc white, shirasu balloon, glassmicro-balloon, organic micro-balloon made of phenol resin or vinylidenechloride resin, PVC powder, PMMA powder, and other resin powders; andfibrous fillers such as asbestos, glass fiber, and filament and thelike. When the filler is used, the use amount thereof is from 1 to 250parts by weight, preferably from 10 to 200 parts by weight for 100 ofthe polymer(s) of the component(s) (A).

As described in JP-A-2001-181532, the filler can be dehydrated and driedin advance by mixing the filler with a dehydrating agent such as calciumoxide and the like into a homogeneous form, putting the mixtureair-tightly into a bag made of an airtight material, and then allowingthe bag to stand still for an appropriate time. By use of this filler,which has a low water content, the storage stability of the compositioncan be improved, in particular, when the composition is rendered aone-part type composition.

When a composition with a high transparency is desired, one can use apolymer powder made of a polymer such as methyl methacrylate and thelike, amorphous silica, or the like, as described in JP-A-11-302527.Moreover, a composition having a high transparency can be obtained byusing, as a filler, hydrophobic silica, which silicon dioxide finepowder is having a surface to which hydrophobic groups are bonded, asdescribed in JP-A-2000-38560. The surface of the silicon dioxide finepowder generally has silanol groups (—SiOH), and the silanol groups arecaused to react with an organic silicon halide, an alcohol or the like,thereby producing (—SiO-hydrophobic group). The resultant product ishydrophobic silica. Specifically, dimethylsiloxane,hexamethyldisilazane, dimethyldichlorosilane, trimethoxyoctylsilane,trimethylsilane or the like reacts with and is bonded to the silanolgroups present in the surface of the silicon dioxide fine powder. Theresultant is hydrophobic silica. Silicon dioxide fine powder having asurface made of silanol groups (—SiOH) is called hydrophilic silica finepowder.

When a cured product with high strength is desired to use of a fillerselected from fume silica, precipitating silica, crystalline silica,fused silica, dolomite, silicic anhydride, hydrated silicic acid, carbonblack, surface-treated fine calcium carbonate, calcined clay, clay,active zinc white, and others can be used in an amount of 1 to 200 partsby weight for 100 parts by weight of the organic polymer(s) (A) having areactive silicon group. When a cured product having a low strength and alarge elongation at break is desired a filler selected from titaniumoxide, a calcium carbonate species such as ground calcium carbonate,magnesium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon,and others can used in an amount of 5 to 200 parts by weight for 100parts by weight of the polymer(s) (A) having a reactive silicon group.As the value of the specific surface area of calcium carbonate islarger, the effect of improving the rupture strength, the elongation atbreak and the adhesiveness of the cured product becomes larger. Ofcourse, these fillers may be used alone or in the form of a mixture oftwo or more thereof. When calcium carbonate is used, it is desired touse surface-treated fine calcium carbonate, and a calcium carbonatespecies having a large particle diameter, such as ground calciumcarbonate and the like, together. The particle diameter of thesurface-treated fine calcium carbonate is preferably 0.5 μm or less, andthe surface treatment is preferably treatment with a fatty acid or afatty acid salt. Moreover, the particle diameter of the calciumcarbonate species having a large particle diameter is preferably 1 μm ormore, and the species not subjected to any surface treatment can beused.

The composition of the present disclosure can be preferably used for: ajoint of outer walls of a building, such as siding boards, inparticular, ceramic siding boards and others; an adhesive agent forouter wall tiles; an adhesive agent, for outer wall tiles, that mayremain as it is in the joint of the walls; or the like since the curedproduct therefrom has good chemical resistance and other properties. Itis desired that the design of outer walls is in harmony with the designof the sealant. The composition is used for high-quality outer wallswhen sputtering paint is used together or colored aggregate isincorporated into the composition.

A tackifier may be added to the composition of the present disclosure.The tackifier of resin (tackifying resin) is not particularly limited,and may be a resin that is usually used whether the resin is in a solidform or in a liquid form at normal temperature. Specific examplesthereof include styrene based block copolymer, a hydrogenated productthereof, phenol resin, modified phenol resins (such as cashew oilmodified phenol resin, tall oil modified phenol resin and the like),terpene-phenol resin, xylene-phenol resin, cyclopentadiene-phenol resin,coumalin-indene resin, rosin resin, rosin ester resin, hydrogenatedrosin ester resin, xylene resin, low molecular weight polystyrene resin,styrene copolymer resin, petroleum resins (such as C₅ hydrocarbon resin,C₉ hydrocarbon resin, C₅-C₉ hydrocarbon copolymer resin and the like),hydrogenated petroleum resins, terpene resin, and DCPD resin petroleumresin and the like. These may be used alone or in combination of two ormore thereof. Examples of the styrene block copolymer and thehydrogenated product thereof include styrene-butadiene-styrene blockcopolymer (SBS), styrene-isoprene-styrene block copolymer (SIS),styrene-ethylenebutylene-styrene block copolymer (SEBS),styrene-ethylenepropylene-styrene block copolymer (SEPS),styrene-isobutylene-styrene copolymer (SIBS) and the like. Thesetackifying resins may be used alone or in combination of two or morethereof.

The tackifying resin is used in an amount of 5 to 1,000 parts by weight,preferably from 10 to 100 parts by weight for 100 parts by weight of theorganic polymer(s) (A).

A solvent or a diluting agent can be added to the composition of thepresent disclosure. The solvent and the diluting agent are notparticularly limited, and the following can be used: aliphatichydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenatedhydrocarbons, alcohols, esters, ketones, ethers and others. When thesolvent or the diluting agent is used, the boiling point of the solventis preferably 150° C. or higher, more preferably 200° C. or higher, inparticular preferably 250° C. or higher in light of a problem of airpollution when the composition is used indoors. The above-mentionedsolvents or diluting agents may be used alone or in combination of twoor more thereof.

Moreover, a silicate can be used in the composition of the presentdisclosure. This silicate acts as a crosslinking agent, and has afunction of improving the restorability, the endurance and the creepresistance of the polymer(s) of the component (A) in the presentdisclosure. Furthermore, the silicate also has a function of improvingthe adhesiveness, the water-resistant adhesiveness, and the adhesionendurance under high temperature and high humidity. As the silicate,tetraalkoxysilane or a partially-hydrolyzed condensation product thereofcan be used. In the case of using the silicate, the use amount thereofis preferably from 0.1 to 20 parts by weight, more preferably from 0.5to 10 parts by weight for 100 parts by weight of the polymer(s) of thecomponent (A).

Specific examples of the silicate include tetraalkoxysilanes(tetraalkylsilicates) such as tetramethoxysilane, tetraethoxysilane,ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane,tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane,tetra-i-butoxysilane, tetra-t-butoxysilane and the like; andpartially-hydrolyzed condensation products thereof.

The partially-hydrolyzed condensation products of tetraalkoxysilanes aremore preferred since their effects of improving the restorability, theendurance and the creep resistance to a greater extent thantetraalkoxysilanes.

Examples of the partially-hydrolyzed condensation products oftetraalkoxysilanes include products each obtained by adding water to atetraalkoxysilane in a usual way, and then hydrolyzing the resultantpartially so as to be condensed. Furthermore, as partially-hydrolyzedcondensation products of organosilicate compounds, commerciallyavailable products can be used. Examples of the condensation productsinclude Methyl Silicate 51 and Ethyl Silicate 40 (each manufactured byColcoat Co., Ltd.).

A plasticizer can be added to the composition of the present disclosure.The addition of the plasticizer makes it possible to adjust theviscosity and the slump property of the curable composition, and thetensile strength, the elongation and other mechanical properties of thecured product obtained by curing the composition. Examples of theplasticizer include phthalic acid esters such as dibutyl phthalate,diheptyl phthalate, bis(2-ethylhexyl) phthalate, butylbenzyl phthalateand the like; non-aromatic bibasic acid esters such as dioctyl adipate,dioctyl sebacate, dibutyl sebacate, isodecyl succinate and the like;aliphatic esters such as butyl oleate, methyl acetylricinolate and thelike; phosphates such as tricresyl phosphate, tributyl phosphate and thelike; trimellitic acid esters; chlorinated paraffins; hydrocarbon oilssuch as alkyldiphenyl, partially-hydrogenated terphenyl and the like;process oils; epoxy plasticizers such as epoxidized soybean oil, benzylepoxystearate and the like.

A polymeric plasticizer can be used. In the case of using the polymericplasticizer, the initial physical properties are maintained over alonger term than in the case of using a low molecular weightplasticizer, which does not contain in the molecule thereof anypolymeric component. Furthermore, when an alkyd paint is painted ontothe cured product, the drying property, which may be calledpaintability, can be improved. Specific examples of the polymericplasticizer include vinyl polymers, which are each obtained bypolymerizing a vinyl monomer by a variety of methods; polyalkyleneglycol esters such as diethylene glycol dibenzoate, triethylene glycoldibenzoate, pentaerythritol esters and the like; polyester plasticizerseach made from a dibasic acid such as sebacic acid, adipic acid, azelaicacid, phthalic acid or the like, and a dihydric alcohol such as ethyleneglycol, diethylene glycol, triethylene glycol, propylene glycol, anddipropylene glycol; polyethers, for example, polyetherpolyols such aspolyethylene glycol and polypropylene glycol polytetraethylene glycol,which has a molecular weight of 500 or more, preferably 1000 or more,and derivatives obtained by changing hydroxyl groups of thesepolyetherpolyols to ester groups or ether groups; polystyrenes such aspolystyrene and poly-α-methylstyrene; polybutadiene; polybutene;polyisobutylene; butadiene-acrylonitrile; and polychloroprene. However,the polymeric plasticizer is not limited thereto.

Out of these polymeric plasticizers, ones compatible with the component(A) are preferred. From this viewpoint, polyethers and vinyl polymersare preferred. When a polyether is used as the plasticizer, the surfacecurability and the depth curability are improved. Moreover, after thecomposition is stored, the composition does not undergo curing delay.Thus, the use is preferred. Out of the plasticizers, polypropyleneglycol is more preferred. From the viewpoint of compatibility, weatherresistance and heat resistance, vinyl polymers are preferred. Out of thevinyl polymers, acrylic polymers and/or methacrylic polymers arepreferred, and acrylic polymers such as poly(alkyl acrylate)s are morepreferred. The method for synthesizing the polymers is preferably aliving radical polymerization method since the molecular weightdistribution is narrow and the viscosity is low. An atomic transferradical polymerization method is more preferred. It is also preferred touse a polymer based on the so-called SGO process, which is obtained bysubjecting an alkyl acrylate monomer described in JP-A-2001-207157 tocontinuous bulk polymerization at high temperature and high pressure.

The number-average molecular weight of the polymeric plasticizer ispreferably from 500 to 15,000, more preferably from 800 to 10,000, evenmore preferably from 1000 to 8,000, in particular preferably from 1,000to 5,000. The molecular weight is most preferably from 1,000 to 3,000.If the molecular weight is too low, the plasticizer flows out with timeby heat or rainfall so that the initial physical properties cannot bemaintained over a long term, the plasticizer causes pollution based onadhesion of dust thereto, and the alkyd paintability cannot be improved.If the molecular weight is too high, the viscosity becomes high so thatthe workability deteriorates. The molecular weight distribution of thepolymeric plasticizer is not particularly limited, and a narrowdistribution is preferred. The distribution is preferably less than1.80, more preferably 1.70 or less, even more preferably 1.60 or less,even more preferably 1.50 or less, in particular preferably 1.40 orless, most preferably 1.30 or less.

In the case that the plasticizer is a polyether polymer, thenumber-average molecular weight is measured by terminal group analysis.In the case that the plasticizer is any other polymer, thenumber-average molecular weight is measured by a GPC method. Themolecular weight distribution (Mw/Mn) is measured by the GPC method (interms of polystyrene).

The polymeric plasticizer may have no reactive silicon group, or mayhave a reactive silicon group. When the plasticizer has a reactivesilicon group, the plasticizer acts as a reactive plasticizer. Thus, theplasticizer can be prevented from being shifted from the cured product.When the plasticizer has a reactive silicon group, the number ofindividuals of the reactive silicon group is preferably 1 or less, morepreferably 0.8 or less per molecule on average. In the case of using aplasticizer having a reactive silicon group, in particular, anoxyalkylene polymer having a reactive silicon group, the number-averagemolecular weight thereof is preferably lower than that of the polymer(s)of the component (A). If not so, plasticizing effect may not beobtained.

About the plasticizer, only one species thereof may be used, or two ormore species thereof may be used together. A low molecular weightplasticizer and a polymeric plasticizer may be used together. Theseplasticizers may be blended when the polymer(s) is/are produced.

The amount of the used plasticizer is from 5 to 150 parts by weight,preferably from 10 to 120 parts by weight, even more preferably from 20to 100 parts by weight for 100 parts by weight of the polymer(s) of thecomponent (A). If the amount is less than 5 parts by weight, effects asa plasticizer are not expressed. If the amount is more than 150 parts byweight, the mechanical strength of the cured product is insufficient.

If necessary, a physical property adjustor for adjusting tensilecharacteristics of the cured product may be added to the curablecomposition of the present disclosure. The physical property adjustor isnot particularly limited, and examples thereof includealkylalkoxysilanes such as methyltrimethoxysilane,dimethyldimethoxysilane, trimethylmethoxysilane,n-propyltrimethoxysilane and the like; alkoxysilanes having anunsaturated group, such as dimethyldiisopropenoxysilane,methyltriisopropenoxysilane, other alkylisopropenoxysilanes,vinyltrimethoxysilane, vinyldimethylmethoxysilane and the like; siliconevanish; polysiloxanes and the like. The use of the physical propertyadjustor makes it possible that when the composition of the presentdisclosure is cured, the hardness is raised or the hardness isconversely lowered so as to improve the property of elongation at break.The above-mentioned physical property adjustors may be used alone or incombination of two or more thereof.

In particular, a compound which can be hydrolyzed, thereby generating acompound having in the molecule thereof a monovalent silanol group hasan effect of lowering the modulus of the cured product withoutdeteriorating the stickiness of the surface of the cured product. Acompound which can generate trimethylsilanol is particularly preferred.Examples of the compound which can be hydrolyzed, thereby generating acompound having in the molecule thereof a monovalent silanol groupinclude compounds described in JP-A-5-17521. Other examples thereofinclude compounds which are each a derivative of an alkylalcohol such ashexanol, octanol, decanol and the like, and can each generate a siliconcompound which can be hydrolyzed, thereby generating R₃SiOH such astrimethylsilanol and the like; and compounds which are each a derivativeof a polyhydric alcohol having 3 or more hydroxyl groups, such astrimethylolpropane, glycerin, pentaerythritol, sorbitol and the like, asdescribed in JP-A-11-241029, and can each generate a silicon compoundwhich can be hydrolyzed, thereby generating R₃SiOH such astrimethylsilanol and the like.

Different examples thereof include compounds which are each a derivativeof an oxypropylene polymer, and can each generate a silicon compoundwhich can be hydrolyzed, thereby generating R₃SiOH such astrimethylsilanol and the like, as described in JP-A-7-258534.Furthermore, there can be used a polymer having a crosslinkable,hydrolyzable silicon-containing group and a silicon-containing groupwhich can be hydrolyzed so as to be converted to amonosilanol-containing compound, as described in JP-A-6-279693.

The physical property adjustor is used in an amount of 0.1 to 20 partsby weight, preferably 0.5 to 10 parts by weight for 100 parts by weightof the organic polymer(s) (A) having a reactive silicon group.

If necessary, a thixotrope (anti-dripping agent) may be added to thecurable composition of the present disclosure to prevent the compositionfrom dripping and to make the workability better. The anti-drippingagent is not particularly limited, and examples thereof includepolyamide waxes; hydrogenated castor oil derivatives; and metal soapssuch as calcium stearate, aluminum stearate, barium stearate and thelike. In the case of using rubber powder having a particle diameter of10 to 500 μm as described in JP-A-11-349916 or an organic fiber asdescribed in JP-A-2003-155389, a composition having a high thixotropyand a good workability can be obtained. These thixotropes (anti-drippingagents) may be used alone or in combination of two or more thereof. Thethixotrope(s) is/are used in an amount of 0.1 to 20 parts by weight for100 parts by weight of organic the polymer(s) (A) having a reactivesilicon group.

In the composition of the present disclosure, a compound having in asingle molecule thereof an epoxy group can be used. When the compoundhaving an epoxy group is used, the restorability of the cured productcan be made high. Examples of the compound having an epoxy group includeepoxidized unsaturated oils and fats, epoxidized unsaturated aliphaticacid esters, alicyclic epoxy compounds, epichlorohydrin derivatives andmixtures thereof, and the like. Specific examples thereof includeepoxidized soybean oil, epoxidized linseed oil,bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS),epoxyoctyl stearate, epoxybutyl stearate and the like. Among them, E-PSis particularly preferred. It is advisable to use the epoxy compound inan amount of 0.5 to 50 parts by weight for 100 parts by weight of theorganic polymer(s) (A) having a reactive silicon group.

In the composition of the present disclosure, a photo-curable materialcan be used. When the photo-curable material is used, a coating of thephoto-curable material is formed on the surface of the cured product.Thus, the stickiness or the weather resistance of the cured product canbe improved. The photo-curable material is a material which undergoes achemical change in molecular structure by action of light so as togenerate a physical change such as curing. As a compound of this type,many materials are known, examples of which include organic monomers,oligomers, resins and compositions containing these materials and thelike. Any commercially available products can be used. Typically, anunsaturated acrylic compound, a polyvinyl cinnamate, an azide resin orthe like can be used. The unsaturated acrylic compound is a monomer oroligomer having one or more acrylic or methacrylic unsaturated groups,or a mixture thereof. Examples thereof include propylene (or butylene orethylene) glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate andthe like, or oligoesters made from such a monomer and having a molecularweight of 10000 or less. In particular, compounds having an acrylicfunctional group are preferred, and compounds each containing in asingle molecule thereof 3 or more acrylic functional groups on averageare preferred.

An oxygen curable material can be used in the composition of the presentdisclosure. Examples of the oxygen curable material include unsaturatedcompounds reactive with oxygen in air. The material reacts with oxygenin air to form a cured coating in the vicinity of the surface of thecured product, thereby fulfilling an act of preventing the stickiness ofthe surface or adhesion of wastes or dust onto the cured productsurface. Specific examples of the oxygen curable material include dryingoils, typical examples of which are tung oil and linseed oil; variousalkyd resins obtained by modifying the compounds; acrylic polymer, epoxyresin, and silicone resin which are each modified with a drying oil;liquid polymers such as 1,2-polybutadiene, 1,4-polybutadiene, C5 to C8diene polymer and the like, which are each obtained by polymerizing orcopolymerizing one or more diene compounds such as butadiene,chloroprene, isoprene, and/or 1,3-pentadiene; liquid copolymers such asNBR, SBR and the like, which are each obtained by copolymerizing amonomer copolymerizable with the diene compounds, such as acrylonitrile,styrene and the like, with one or more of the diene compounds so as tomake the diene compound(s) into one or more main components; and variousmodified products thereof (such as maleic acid modified products boiledoil modified products and the like). These may be used or in combinationof two or more thereof. Among them, tung oil and liquid diene polymersare particularly preferred. When a catalyst for promoting theoxidization curing reaction or a metal drier is used together, theadvantageous effects may be enhanced. Examples of the catalyst or metaldrier include metal salts such as cobalt naphthenate, lead naphthenate,zirconium naphthenate, cobalt octanoate, zirconium octanonate and thelike; and amine compounds and the like. The use amount of the oxygencurable material is preferably from 0.1 to 20 parts by weight, morepreferably 0.5 to 10 parts by weight for 100 parts by weight of theorganic polymer(s) (A) having a reactive silicon group. If the useamount is less than 0.1 part by weight, an improvement in pollutionresistance is insufficient. If the amount is more than 20 parts byweight, the tensile characteristic or the like of the cured producttends to be damaged.

An antioxidant can be used in the composition of the present disclosure.When the antioxidant is used, the heat resistance of the cured productcan be enhanced. Examples of the antioxidant include hindered phenols,monophenols, bisphenols, and polyphenols. Particularly preferred arehindered phenols. Similarly, the following can also be used: a hinderedamine photostabilizer named TINUVIN 622LD, TINUVIN 144, CHIMASSORB944LD, or CHIMASSORB 119FL (BASF.); MARK LA-57, MARK LA-62, MARK LA-67,MARK LA-63, or MARK LA-68 (Asashi Denka) SANOL LS-770, SANOL LS-765,SANOL LS-292, SANOL LS-2626, SANOL LS-1114, or SANOL LS-744 (Sankyo Co.,Ltd.). The use amount of the antioxidant is preferably from 0.1 to 10parts by weight, more preferably from 0.2 to 5 parts by weight for 100parts by weight of the organic polymer(s) (A) having a reactive silicongroup.

A photostabilizer can be used in the composition of the presentdisclosure. The use of the photostabilizer makes it possible to preventthe cured product form being deteriorated by photo-oxidation. Examplesof the photostabilizer include benzophenones, benzotriazoles, triazinesand hindered amine light stabilizers compounds, and the like. The useamount of the photostabilizer is preferably from 0.1 to 10 parts byweight, more preferably from 0.2 to 5 parts by weight for 100 parts byweight of the organic polymer(s) (A) having a reactive silicon group.

In the case of using the photocurable material, in particular, anunsaturated acrylic compound together in the composition of the presentdisclosure, it is preferred to use a tertiary-amine-containing hinderedamine photostabilizer as a hindered amine photostabilizer, as describedin JP-A-5-70531, in order to improve the storage stability of thecomposition. Examples of the tertiary-amine-containing hindered aminephotostabilizer include photostabilizers named TINUVIN 622LD, TINUVIN144, and CHIMASSORB 119FL (each manufactured by BASF.); MARK LA-57, MARKLA-62, MARK LA-67, and MARK LA-63 (each manufactured by Asashi DenkaKogyo K.K.); and SANOL LS-765, SANOL LS-292, SANOL LS-2626, SANOLLS-1114, SANOL LS-744 (each manufactured by Sankyo Co., Ltd.) and thelike.

An ultraviolet absorber can be used in the composition of the presentdisclosure. The use of the ultraviolet absorber makes it possible toenhance the surface weather resistance of the cured product. Examples ofthe ultra violet absorber include benzophenone compounds, benzotriazolecompounds, salicylate compounds, substituted tolyl compounds, metalchelate compounds and the like. Particularly preferred are benzotriazolecompounds. The use amount of the ultraviolet absorber is preferably from0.1 to 10 parts by weight, more preferably from 0.2 to 5 parts by weightfor 100 parts by weight of the organic polymer(s) (A) having a reactivesilicon group. It is preferred to use a phenolic or hindered phenolicantioxidant with a hindered amine photostabilizer, and a benzotriazoleultraviolet absorber together.

An epoxy resin can be added to the composition of the presentdisclosure. The composition to which the epoxy resin is added isparticularly preferred as an adhesive, in particular, as an adhesive forouter wall tiles. Examples of the epoxy resin includeepichlorohydrin-bisphenol A epoxy resin, epichlorohydrin-bisphenol Fepoxy resin, glycidyl ether of tetrabromobisphenol A, other flameretardant epoxy resins, novolak epoxy resin, hydrogenated bisphenol Aepoxy resin, glycidyl ether type epoxy resin of a bisphenol A propyleneoxide adduct, glycidyl etherester type epoxy resin of p-oxybenzoic acid,m-aminophenol epoxy resin, diaminodiphenylmethane epoxy resin,urethane-modified epoxy resin, various alicyclic epoxy resins,N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine, triglycidylisocyanurate, polyalkylene glycol diglycidyl ether, glycerin, otherglycidyl ethers of polyhydric alcohol, hydantoin type epoxy resin,petroleum resin, and other epoxidized unsaturated polymers. However, theepoxy resin is not limited thereto, and any epoxy resin that isordinarily used can be used. Preferred is an epoxy resin having, in themolecule thereof, at least two epoxy groups since a high reactivity isexhibited when the resin is cured and a three-dimensional networkstructure is easily formed in the cured product. More preferred isbisphenol A epoxy resin, novolak epoxy resin or the like. The ratio byweight of the used epoxy resin to the organic polymer(s) (A) having areactive silicon group ranges from 100/1 to 1/100. If the ratio of the(A) to the epoxy resin is less than 1/100, the impact strength of theepoxy resin cured product or the toughness-improving effect thereof isnot easily obtained. If the ratio of the (A)/to the epoxy resin is morethan 100/1, the strength of the organic polymer cured product becomesinsufficient. A preferred use ratio there between is not decided withoutreservation since the ratio is varied in accordance with the usage ofthe curable resin composition, or the like. In the case of improving,for example, the impact resistance, flexibility, toughness, peelstrength or the like of the epoxy resin cured product, the component (A)is/are used preferably in an amount of 1 to 100 parts by weight, morepreferably in an amount of 5 to 100 parts by weight for 100 parts byweight of the epoxy resin. In the case of improving the strength of thecured product of the component(s) (A), the epoxy resin is usedpreferably in an amount of 1 to 200 parts by weight, more preferably inan amount of 5 to 100 parts by weight for 100 parts by weight of thecomponent (A).

In the case of the addition of the epoxy resin, a curing agent forcuring the epoxy resin can be used in the curable composition of thepresent disclosure. The epoxy resin curing agent which can be used isnot particularly limited, and may be any epoxy resin curing agent thatis ordinarily used. Specific examples thereof include primary andsecondary amines such as triethylenetetramine, tetraethylenepentamine,diethylaminopropylamine, N-aminoethylpiperidine, m-xylylenediamine,m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone,isophoronediamine, amine-terminated polyether and the like; tertiaryamines such as 2,4,6-tris(dimethylaminomethyl)phenol and tripropylamine,and salts of these tertiary amines; polyamide resins; imidazoles;dicyandiamines; trifluoroboron complex compounds; carboxylic anhydridessuch as phthalic anhydride, hexahydrophthalic anhydride,tetrahydrophthalic anhydride, dodecylsuccinic anhydride, pyromelliticanhydride, chlorendic anhydride and the like; alcohols; phenols;carboxylic acids; and diketone complex compounds of aluminum orzirconium, and the like. However, the curing agent is not limitedthereto. The above-mentioned curing agents may be used alone or incombination of two or more thereof.

When the epoxy resin curing agent is used, the use amount thereof rangesfrom 0.1 to 300 parts by weight for 100 parts by weight of the epoxyresin.

A ketimine can be used as the epoxy resin curing agent. The ketimine isstably present in a state that there is no water content, and isdissolved into a primary amine and a ketone by water content. Theresultant primary amine becomes a curing agent for epoxy resin which canbe cured at room temperature. When the ketimine is used, a one-part typecomposition can be obtained. Such a ketimine compound can be obtained bycondensation reaction between an amine compound and a carbonyl compound.

In order to synthesize the ketimine, a known amine compound and a knowncarbonyl compound may be used. As the amine compound, the following isused: a diamine such as ethylenediamine, propylenediamine,trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane,2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane,hexamethylenediamine, p-phenylenediamine, p,p′-biphenylenediamine or thelike; a polyhydric amine such as 1,2,3-triaminopropane, triaminobenzene,tris(2-aminoethyl)amine, tetrakis(aminomethyl)methane or the like; apolyalkylenepolyamine such as diethylenetriamine, triethylenetriamine,tetraethylenepentamine or the like; a polyoxyalkylene polyamine; anaminosilane such as γ-aminopropyltriethoxysilane,N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane,N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane; or the like. As thecarbonyl compound, the following can be used: an aldehyde such asacetoaldehyde, propionaldehyde, n-butylaldehyde, isobutylaldehyde,diethylacetoaldehyde, glyoxal, benzaldehyde or the like; a cyclic ketonesuch as cyclopentanone, trimethylcyclopentanone, cyclohexanone,trimethylcyclohexanone or the like; an aliphatic ketone such as acetone,methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone,methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropylketone, dibutyl ketone, diisobutyl ketone or the like; a β-dicarbonylcompound such as acetylacetone, methyl acetoacetate, ethyl acetoacetate,dimethyl malonate, diethyl malonate, methylethyl malonate,dibenzoylmethane; or the like.

When an imino group is present in the ketimine, the imino group may becaused to react with styrene oxide, a glycidyl ether such as butylglycidyl ether allyl glycidyl ether or the like, a glycidyl ester, orthe like. The above-mentioned ketimines may be used alone or incombination of two or more thereof. The use amount thereof is from 1 to100 parts by weight for 100 parts by weight of the epoxy resin, and isvaried in accordance with the kind of the epoxy resin and that of theketimine.

A flame retardant may be added to the curable composition of the presentdisclosure, examples of the retardant including a phosphorus-containingplasticizer such as ammonium polyphosphate, tricresyl phosphate or thelike; aluminum hydroxide, magnesium hydroxide, or thermally expandablegraphite or the like. These flame retardants may be used alone or incombination of two or more thereof.

The flame retardant is used in an amount of 5 to 200 parts by mass,preferably 10 to 100 parts by mass for 100 parts by weight of thecomponent (A).

If necessary, various additives may be added to the curable compositionof the present disclosure in order to adjust various physical propertiesof the curable composition or the cured product. Examples of theadditives include a curability adjustor, a radical inhibitor, a metaldeactivator agent, an ozone deterioration preventive, aphosphorus-containing peroxide decomposer, a lubricant, a pigment, afoaming agent, an ant preventive, and an antifungal agent. Theseadditives may be used alone or in combination of two or more thereof.Specific examples of additives other than the specific examples of theadditives described in the specification are described in JP-B-4-69659and 7-108928, and JP-A-63-254149, 64-22904 and 2001-72854, and otherpublications.

The curable composition of the present disclosure can be prepared into aone component form, wherein all blend components are beforehand blended,air-tightly sealed up and stored, and after the resultant blend isactually used, the blend is cured with moisture in the air.Alternatively, the composition can be prepared into a two-componentform, wherein a curing catalyst, a filler, a plasticizer, water andother components are separately blended with each other as a curingagent, and this blend and a polymer composition are mixed before used.From the viewpoint of workability, the one-part form is preferred.

In the case that the curable composition is in a one component form, allof the blend components are beforehand blended with each other;therefore, it is preferred to use the blend components which containwater content after the components are dehydrated and dried in advance,or dehydrate the composition by pressure-reduction when the componentsare blended and kneaded. In the case that the curable composition is ina two-component form, it is unnecessary to blend a curing catalyst withthe main agent containing the polymer(s) having a reactive silicongroup; therefore, it is hardly feared that the blend components aregelatinized even if the components contain a certain amount of watercontent. However, in the case that the composition is required to havestorage stability for a long term, the composition is preferablydehydrated and dried. Preferred examples of the method for thedehydration and drying include a heating drying method when thecomposition is in the form of a solid such as powder; and apressure-reducing dehydrating method or a dehydrating method usingsynthetic zeolite, activated alumina, silica gel, caustic lime,magnesium oxide or the like when the composition is in a liquid form. Itis allowable to incorporate a small amount of an isocyanate compoundinto the composition to cause the isocyanate group to react with water,thereby attaining dehydration, or to incorporate an oxazolidine compoundsuch as 3-ethyl-2-methyl-2-(3-methylbutyl)-1,3-oxazolidine or the liketo cause the compound to react with water, thereby attainingdehydration. By the addition of the following compound besides thisdehydration drying method, the storage stability is made better byadding the following compound: a lower alcohol such as methanol orethanol; or an alkoxysilane compound such as n-propyltrimethoxysilane,vinyltrimethoxysilane, vinylmethyldimethoxysilane, methyl silicate,ethyl silicate, γ-mercaptopropylmethyldimethoxysilane,γ-mercaptopropylmethyldiethoxysilane or the like.

The use amount of the dehydrating agent, in particular, a siliconcompound reactive with water, such as vinyltrimethoxysilane or the like,is preferably from 0.1 to 20 parts by weight, more preferably from 0.5to 10 parts by weight for 100 parts by weight of the organic polymer(s)(A) having a reactive silicon group.

The method for preparing the curable composition of the presentdisclosure is not particularly limited, and a usual method is adopted,an example of the method being a method of blending the above-mentionedcomponents with each other, then using a mixer, a roll, a kneader or thelike to knead the blend at normal temperature or while the blend isheated, or a method of using a small amount of an appropriate solvent todissolve the above-mentioned components therein, and then mixing thecomponents, or other methods.

When the curable composition of the present disclosure is exposed to theatmosphere, the composition forms a three-dimensional network structureby action of water, so as to be cured into a solid having rubber-likeelasticity.

The curable composition of the present disclosure can be used for abinder, a sealing agent for a building, ship, car, road or the like, anadhesive, a mold or pattern-forming material, a vibration isolatingmaterial, a vibration reducing material, a soundproof material, afoaming material, a paint, a spraying material, and so on. Thecomposition is more preferably used as a sealant or an adhesive, out ofthe above-mentioned materials, since the cured product obtained bycuring the curable composition of the present disclosure is excellent inflexibility and adhesiveness.

The curable composition can be used for various articles, such aselectrical/electronic part materials such as a solar cell rear facesealant and the like, electrically insulating materials such as aninsulating coating material for electric wires/cables and the like,elastic adhesives, contact-type adhesives, spray type sealants, crackrepairing materials, tile-laying adhesives, powdery paints, castingmaterials, rubber materials for medical treatment, adhesives for medicaltreatment, medical instrument sealants, food wrapping materials, jointsealants for outer packaging materials such as a siding board and thelike, coating materials, primers, electromagnetic-wave-shieldingelectroconductive materials, thermally conductive materials, hot meltmaterials, electrical and electronic potting agents, films, gaskets,various molding materials, rust resisting/waterproof sealants for an endface (cut portion) of net-incorporated glass or laminated glass, andliquid sealants used in automobile parts, electrical parts, or variousmechanical parts. Furthermore, the curable composition can adhereclosely to various substrates such as glass, ceramic, wood, metal, resinmolded product substrates and the like by itself or by aid of a primer;therefore, the curable composition can also be used as various types ofsealing compositions or adhesive compositions. Moreover, the curablecomposition of the present disclosure can be used as an adhesive forinterior panels, an adhesive for exterior panels, a tile-layingadhesive, a stone-material-laying adhesive, a ceiling finishingadhesive, a floor finishing adhesive, a wall finishing adhesive, anadhesive for automobile panels, an electrical/electronic/precisioninstrument fabricating adhesive, a direct grading sealants, a sealantfor double glazing, a sealant for the SSG method, or a sealant forworking joints of a building.

The polymer component (A) may be a liquid or solid-based polymer havinga reactive terminal silyl group. The polymer component (A) is notparticularly limited and may be chosen from any cross-linkable polymeras may be desired for a particular purpose or intended use. Non-limitingexamples of suitable polymers for the polymer component (A) includepolyorganosiloxanes (P₁) or organic polymers free of siloxane bonds(P₂), wherein the polymers (P₁) and (P₂) comprise reactive terminalsilyl groups. In one embodiment, the polymer component (A) may bepresent in an amount of from about 10 to about 100 wt. % of the curablecomposition. In one embodiment, the curable composition comprises about100 parts of the polymer component (A).

As described above, the polymer component (A₁) may include a wide rangeof polyorganosiloxanes. In one embodiment, the polymer component maycomprise one or more polysiloxanes and copolymers of formula:(R¹ _(a)R² _(3-a)Si—Z—)_(n)—X—Z—SiR¹ _(a)R² _(3-a)  (3a)

R¹ may be chosen from saturated C₁-C₁₂ alkyl, which can be substitutedwith one or more of a halogen e.g., Cl or F, an O, S or N atom, C₅-C₁₆cycloalkyl, C₂-C₁₂ alkenyl, C₇-C₁₆ arylalkyl, C₇-C₁₆ alkylaryl, phenyl,C₂-C₄ polyalkylene ether, or a combination of two or more thereof, e.g.,methyl, trifluoropropyl and/or phenyl groups.

R² may be a group reactive to protonated agents such as water and may bechosen from OH, C₁-C₈-alkoxy, C₂-C₁₈-alkoxyalkyl, amino, alkenyloxy,oximoalkyl, enoxyalkyl, aminoalkyl, carboxyalkyl, amidoalkyl, amidoaryl,carbamatoalkyl or a combination of two or more thereof. Exemplary groupsfor R² include OH, alkoxy, alkenyloxy, alkyloximo, alkylcarboxy,alkylamido, arylamido, or a combination of two or more thereof.

Z may be a bond, a divalent linking unit selected from the group ofO_(1/2), hydrocarbons which can contain one or more O, S or N atom,amide, urethane, ether, ester, urea units or a combination of two ormore thereof. If the linking group Z is a hydrocarbon group then Z islinked to the silicon atom over a SiC bond. In one embodiment Z ischosen from a C₁-C₁₄ alkylene.

X is chosen from a polyurethane; a polyester; a polyether; apolycarbonate; a polyolefin; a polypropylene; a polyesterether; and apolyorganosiloxane having units of R₃SiO_(1/2), R₂SiO, RSiO_(3/2),and/or SiO_(4/2), where R is chosen from a C₁-C₁₀-alkyl; a C₁-C₁₀ alkylsubstituted with one or more of Cl, F, N, O or S; a phenyl; a C₇-C₁₆alkylaryl; a C₇-C₁₆ arylalkyl; a C₂-C₄ polyalkylene ether; or acombination of two or more thereof X may be a divalent or multivalentpolymer unit selected from the group of siloxy units linked over oxygenor hydrocarbon groups to the terminal silyl group comprising thereactive group R² as described above, polyether, alkylene, isoalkylene,polyester or polyurethane units linked over hydrocarbon groups to thesilicon atom comprising one or more reactive groups R² as describedabove. The hydrocarbon group X can contain one or more heteroatoms suchas N, S, O or P forming amides, esters, ethers urethanes, esters, ureas.In one embodiment, the average polymerization degree (P_(n)) of X shouldbe more than 6, e.g. polyorganosiloxane units of R₃SiO_(1/2), R₂SiO,RSiO_(3/2), and/or SiO_(4/2). In formula (3), n is 0-100, e.g., 1; and ais 0-2, e.g., 0-1.

Non-limiting examples of the components for unit X includepolyoxyalkylene polymers such as polyoxyethylene, polyoxypropylene,polyoxybutylene, polyoxyethylene-polyoxypropylene copolymer,polyoxytetramethylene, or polyoxypropylene-polyoxybutylene copolymer;ethylene-propylene copolymer, polyisobutylene, polychloroprene,polyisoprene, polybutadiene, copolymer of isobutylene and isoprene,copolymers of isoprene or butadiene and acrylonitrile and/or styrene, orhydrocarbon polymer such as hydrogenated polyolefin polymers produced byhydrogenating these polyolefin polymers; polyester polymer manufacturedby a condensation of dibasic acid such as adipic acid or phthalic acidand glycol, polycarbonates, or ring-opening polymerization of lactones;polyacrylic acid ester produced by radical polymerization of a monomersuch as C₂-C₈-alkyl acrylates, vinyl polymers, e.g., acrylic acid estercopolymer of acrylic acid ester such as ethyl acrylate or butyl acrylateand vinyl acetate, acrylonitrile, methyl methacrylate, acrylamide orstyrene; graft polymer produced by polymerizing the above organicpolymer with a vinyl monomer; polysulfide polymer; polyamide polymersuch as Nylon 6 produced by ring-opening polymerization ofε-caprolactam, Nylon 6.6 produced by polycondensation ofhexamethylenediamine and adipic acid, Nylon 12 produced by ring-openingpolymerization of ε-aminolauro-lactam, copolymeric polyamides,polyurethanes, or polyureas.

Particularly suitable polymers include, but are not limited to,polysiloxanes, polyoxyalkylenes, saturated hydrocarbon polymers such aspolyisobutylene, hydrogenated polybutadiene and hydrogenatedpolyisoprene, or polyethylene, polypropylene, polyester, polycarbonates,polyurethanes, polyurea polymers and the like. Furthermore, saturatedhydrocarbon polymer, polyoxyalkylene polymer and vinyl copolymer areparticularly suitable due to their low glass transition temperaturewhich provide a high flexibility at low temperatures, i.e. below 0° C.

The reactive silyl groups in formula(R¹ _(a)R² _(3-a)Si—Z—)_(n)—X—Z—SiR¹ _(a)R² _(3-a)can be introduced by employing silanes containing a functional groupwhich has the ability to react by known methods with unsaturatedhydrocarbons via hydrosilylation, or reaction of SiOH, aminoalkyl,HOOC-alkyl, HO-alkyl or HO-aryl, HS-alkyl or -aryl, Cl(O)C-alkyl or-aryl, epoxyalkyl or epoxycycloalkyl groups in the prepolymer to belinked to a reactive silyl group via condensation or ring-openingreactions. Examples of the main embodiments include the following: (i)siloxane prepolymers having a SiOH group that can undergo a condensationreaction with a silane (L-group)SiR¹ aR² _(3-a) whereby a siloxy bondSi—O—SiR¹ _(a)R² _(3-a) is formed while the addition product of theleaving group (L-group) and hydrogen is released (L-group +H); (ii)silanes having an unsaturated group that is capable of reacting via ahydrosilylation or a radical reaction with a SiH group or radicallyactivated groups of a silane such as SiH or an unsaturated group; and(iii) silanes including organic or inorganic prepolymers having OH, SH,amino, epoxy, —COCl, —COOH groups, which can react complementarily withepoxy, isocyanato, OH, SH, cyanato, carboxylic halogenides, reactivealkylhalogenides, lactones, lactams, or amines, that is to link thereactive prepolymer with the organofunctional silanes to yield a silylfunctional polymer.

Silanes suitable for method (i) include alkoxysilanes, especiallytetraalkoxysilanes, di- and trialkoxysilanes, di- and triacetoxysilanes,di- and triketoximatosilanes, di- and trialkenyloxysilanes, di- andtricarbonamidosilanes, wherein the remaining residues at the siliconatom of the silane are substituted or unsubstituted hydrocarbons. Othernon-limiting silanes for method (i) include alkyltrialkoxysilanes, suchas vinyltrimethoxysilane, methyltrimethoxysilane, propyltrimethoxysilaneaminoalkyltrimethoxysilane, ethyltriacetoxysilane, methyl- orpropyltriacetoxysilane, methyltributanonoximosilane,methyltripropenyloxysilane, methyltribenzamidosilane, ormethyltriacetamidosilane. Prepolymers suitable for reaction under method(i) are SiOH-terminated polyalkylsiloxanes, which can undergo acondensation reaction with a silane having hydrolysable groups attachedto the silicon atom. Exemplary SiOH-terminated polyalkydisiloxanesinclude polydimethylsilaxanes.

Suitable silanes for method (ii) include alkoxysilanes, especiallytrialkoxysilanes (HSi(OR)₃) such as trimethoxysilane, triethoxysilane,methyldiethoxysilane, methyldimethoxysilane, and phenyldimethoxysilane;methyldiacetoxysilane and phenyldiacetoxysilane. Hydrogenchlorosilanesare in principle possible but are less desirable due to the additionalreplacement of the halogen through an alkoxy or acetoxy group. Othersuitable silanes include organofunctional silanes having unsaturatedgroups which can be activated by radicals, such as vinyl, allyl,mercaptoalkyl, or acrylic groups. Non-limiting examples includevinyltrimethoxysilane, mercaptopropyltrimethoxysilane,methacryloxypropyltrimethoxysilane. Prepolymers suitable for reactionunder method (ii) include vinyl terminated polyalkylsiloxanes,preferably polydimethylsiloxanes, hydrocarbons with unsaturated groupswhich can undergo hydrosilylation or can undergo radically inducedgrafting reactions with a corresponding organofunctional group of asilane comprising, for example, unsaturated hydrocarbon or a —SiH group.

Another method for introducing silyl groups into hydrocarbon polymerscan be the copolymerization of unsaturated hydrocarbon monomers with theunsaturated groups of silanes. The introduction of unsaturated groupsinto a hydrocarbon prepolymer may include, for example, the use ofalkenyl halogenides as chain stopper after polymerization of the siliconfree hydrocarbon moiety.

Desirable reaction products between the silanes and prepolymers includethe following structures:—SiR₂O—SiR₂—CH₂—CH₂—SiR¹ _(a)R² _(3-a), or (hydrocarbon)-[Z—SiR¹ _(a)R²_(3-a)]₁₋₅₀

Suitable silanes for method (iii) include, but are not limited to,alkoxysilanes, especially silanes having organofunctional groups to bereactive to —OH, —SH, amino, epoxy, —COCl, or —COOH.

In one embodiment, these silanes have an isocyanatoalkyl group such asγ-isocyanatopropyltrimethoxysilane,γ-isocyanatopropylmethyldimethoxysilane,γ-isocyanatopropyltriethoxysilane,γ-glycidoxypropylethyldimethoxysilane,γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane,γ-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,epoxylimonyltrimethoxysilane,N-(2-aminoethyl)-aminopropyltrimethoxysilane,γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane,γ-aminopropylmethyldimethoxysilane, orγ-aminopropylmethyldiethoxysilane.

In one embodiment blocked amines or isocyanates (Z′—X)_(n)—Z′ areselected for carrying out first a complete mixing and then the followingcoupling reaction. Examples of blocking agents are disclosed in EP0947531 and other blocking procedures that employ heterocyclic nitrogencompounds such as caprolactam or butanone oxime, or cyclic ketonesreferred to in U.S. Pat. No. 6,827,875 both of which are incorporatedherein by reference in their entirety.

Examples of suitable prepolymers for a reaction under method (iii)include, but are not limited to, polyalkylene oxides having OH groups,preferably with a high molecular weight (M_(w)) (weight averagemolecular weight >6000 g/mol) and a polydispersity M_(w)/M_(n) of lessthan 1.6; urethanes having remaining NCO groups, such as NCOfunctionalized polyalkylene oxides, especially blocked isocyanates.Prepolymers selected from the group of hydrocarbons having —OH, —COOH,amino, epoxy groups, which can react complementarily with an epoxy,isocyanato, amino, carboxyhalogenide or halogenalkyl group of thecorresponding silane having further reactive groups useful for the finalcure.

Suitable isocyanates for the introduction of a NCO group into apolyether may include toluene diisocyanate, diphenylmethanediisocyanate, or xylene diisocyanate, or aliphatic polyisocyanate suchas isophorone diisocyanate, or hexamethylene diisocyanate.

The polymerization degree of the unit X depends on the requirements ofviscosity and mechanical properties of the cured product. If X is apolydimethylsiloxane unit, the average polymerization degree based onthe number average molecular weight M_(n) is preferably 7 to 5000 siloxyunits, preferably 200-2000 units. In order to achieve a sufficienttensile strength of >5 MPa, an average polymerization degree P_(n)of >250 is suitable whereby the polydimethylsiloxanes have a viscosityof more than 300 mPas at 25° C. If X is a hydrocarbon unit other than apolysiloxane unit, the viscosity with respect to the polymerizationdegree is much higher.

Examples of the method for synthesizing a polyoxyalkylene polymerinclude, but are not limited to, a polymerization method using an alkalicatalyst such as KOH, a polymerization method using a transition metalcompound porphyrin complex catalyst such as complex obtained by reactingan organoaluminum compound, a polymerization method using a compositemetal cyanide complex catalyst disclosed, e.g., in U.S. Pat. Nos.3,427,256; 3,427,334; 3,278,457; 3,278,458; 3,278,459; 3,427,335;6,696,383; and 6,919,293.

If the group X is selected from hydrocarbon polymers, then polymers orcopolymers having isobutylene units are particularly desirable due toits physical properties such as excellent weatherability, excellent heatresistance, and low gas and moisture permeability.

Examples of the monomers include olefins having 4 to 12 carbon atoms,vinyl ether, aromatic vinyl compound, vinylsilanes, and allylsilanes.Examples of the copolymer component include 1-butene, 2-butene,2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene,hexene, vinylcyclohexene, methyl vinyl ether, ethyl vinyl ether,isobutyl vinyl ether, styrene, alpha-methylstyrene, dimethylstyrene,beta-pinene, indene, and for example, but not limited to,vinyltrialkoxysilanes, e.g. vinyltrimethoxysilane,vinylmethyldichlorosilane, vinyldimethylmethoxysilane,divinyldichlorosilane, divinyldimethoxysilane, allyltrichlorosilane,allylmethyldichlorosilane, allyldimethylmethoxysilane,diallyldichlorosilane, diallyldimethoxysilane,gamma-methacryloyloxypropyltrimethoxysilane, andgamma-methacryloyloxy-propylmethyldimethoxysilane.

In one embodiment, the polymer component (A) may be a polymer offormula:R² _(3-a)R¹ _(a)Si—Z—[R₂SiO]_(x)[R¹ ₂SiO]_(y)—Z—SiR¹ _(a)R² _(3-a)  (4a)where R¹, R², and Z are defined as above with respect to formula (3a); Ris C₁-C₆-alkyl (an exemplary alkyl being methyl); a is 0-2, x is 0 toabout 10,000; preferably 11 to about 2500; and y is 0 to about 1,000;preferably 0 to 500. In one embodiment, Z in a compound of formula (4a)is a bond or a divalent C₂ to C₁₄-alkylene group, especially preferredis —C₂H₄—.

Non-limiting examples of suitable polysiloxane-containing polymers (P₁)include, for example, silanol-stopped polydimethylsiloxane, silanol oralkoxy-stopped polyorganosiloxanes, e.g., methoxystoppedpolydimethylsiloxane, alkoxy-stoppedpolydimethylsiloxane-polydiphenylsiloxane copolymer, and silanol oralkoxy-stopped fluoroalkyl-substituted siloxanes such as poly(methyl3,3,3-trifluoropropyl)siloxane and poly(methyl3,3,3-trifluoropropyl)siloxane-polydimethyl siloxane copolymer. Thepolyorganosiloxane component (P₁) may be present in an amount of about10 to about 90 wt. % of the composition or 100 pt. wt. In one preferredembodiment, the polyorganosiloxane component has an average chain lengthin the range of about 10 to about 2500 siloxy units, and the viscosityis in the range of about 10 to about 500,000 mPas at 25° C.

Alternatively, the composition may include silyl-terminated organicpolymers (P₂) that are free of siloxane units, and which undergo curingby a condensation reaction comparable to that of siloxane containingpolymers (P₁). Similar to the polyorganosiloxane polymer (P₁), theorganic polymers (P₂) that are suitable as the polymer component (A₁)include a terminal silyl group. In one embodiment, the terminal silylgroup may be of the formula (5):—SiR¹ _(d)R² _(3-d)  (5a)where R¹, R², and a are as defined above.

Examples of suitable siloxane free organic polymers include, but are notlimited to, silylated polyurethane (SPUR), silylated polyester,silylated polyether, silylated polycarbonate, silylated polyolefins likepolyethylene, polypropylene, silylated polyesterether and combinationsof two or more thereof. The siloxane-free organic polymer may be presentin an amount of from about 10 to about 90 wt. % of the composition orabout 100 pt. wt.

In one embodiment, the polymer component (A₁) may be a silylatedpolyurethane (SPUR). Such moisture curable compounds are known in theart in general and can be obtained by various methods including (i)reacting an isocyanate-terminated polyurethane (PUR) prepolymer with asuitable silane, e.g., one possessing both hydrolyzable functionality atthe silicon atom, such as an alkoxy and secondly an activehydrogen-containing functionality, such as mercaptan, primary orsecondary amine, preferably the latter, or by (ii) reacting ahydroxyl-terminated PUR (polyurethane) prepolymer with a suitableisocyanate-terminated silane, e.g., one possessing one to three alkoxygroups. The details of these reactions, and those for preparing theisocyanate-terminated and hydroxyl-terminated PUR prepolymers employedtherein can be found in, amongst others: U.S. Pat. Nos. 4,985,491;5,919,888; 6,207,794; 6,303,731; 6,359,101; and 6,515,164 and publishedU.S. Publication Nos. 2004/0122253 and U.S. 2005/0020706(isocyanate-terminated PUR prepolymers); U.S. Pat. Nos. 3,786,081 and4,481,367 (hydroxyl-terminated PUR prepolymers); U.S. Pat. Nos.3,627,722; 3,632,557; 3,971,751; 5,623,044; 5,852,137; 6,197,912; and6,310,170 (moisture-curable SPUR (silane modified/terminatedpolyurethane) obtained from reaction of isocyanate-terminated PURprepolymer and reactive silane, e.g., aminoalkoxysilane); and, U.S. Pat.Nos. 4,345,053; 4,625,012; 6,833,423; and published U.S. Publication No.2002/0198352 (moisture-curable SPUR obtained from reaction ofhydroxyl-terminated PUR prepolymer and isocyanatosilane). The entirecontents of the foregoing U.S. patent documents are incorporated byreference herein. Other examples of moisture curable SPUR materialsinclude those described in U.S. Pat. No. 7,569,653, the disclosure ofwhich is incorporated by reference in its entirety.

The polysiloxane composition may further include a crosslinker or achain extender as component (C). In one embodiment, the crosslinker isof the formula (6a):R¹ _(a)SiR² _(4-a)  (6a)wherein R² may be as described above, R¹ may be as described above, anda is 0-3. Alternatively, the cross-linker component may be acondensation product of formula (6a) wherein one or more but not all R²groups are hydrolyzed and released in the presence of water and thenintermediate silanols undergo a condensation reaction to give a Si—O—Sibond and water. The average polymerization degree can result in acompound having 2-10 Si units.

As used herein, the term crosslinker includes a compound including anadditional reactive component having at least two hydrolysable groupsand less than three silicon atoms per molecule not defined under (A₁).In one embodiment, the crosslinker or chain extender may be chosen froman alkoxysilane, an alkoxysiloxane, an oximosilane, an oximosiloxane, anenoxysilane, an enoxysiloxane, an aminosilane, a carboxysilane, acarboxysiloxane, an alkylamidosilane, an alkylamidosiloxane, anarylamidosilane, an arylamidosiloxane, an alkoxyaminosilane, analkaryaminosiloxane, an alkoxycarbamatosilane, analkoxycarbamatosiloxane, an imidatosilane, a ureidosilane, anisocyanatosilane, a thioisocyanatosilane, and combinations of two ormore thereof. Examples of suitable cross-linkers include, but are notlimited to, tetraethylorthosilicate (TEOS); methyltrimethoxysilane(MTMS); methyltriethoxysilane; vinyltrimethoxysilane;vinyltriethoxysilane; methylphenyldimethoxysilane;3,3,3-trifluoropropyltrimethoxysilane; methyltriacetoxysilane;vinyltriacetoxysilane; ethyltriacetoxysilane; di-butoxydiacetoxysilane;phenyltripropionoxysilane; methyltris(methylethylketoxime)silane;vinyltris(methylethylketoxime)silane;3,3,3-trifluoropropyltris(methylethylketoxime)silane;methyltris(isopropenoxy)silane; vinyltris(isopropenoxy)silane;ethylpolysilicate; dimethyltetraacetoxydisiloxane;tetra-n-propylorthosilicate; methyldimethoxy(ethylmethylketoximo)silane;methylmethoxybis-(ethylmethylketoximo)silane;methyldimethoxy(acetaldoximo)silane;methyldimethoxy(N-methylcarbamato)silane;ethyldimethoxy(N-methylcarbamato)silane;methyldimethoxyisopropenoxysilane; trimethoxyisopropenoxysilane;methyltri-iso-propenoxysilane; methyldimethoxy(but-2-ene-2-oxy)silane;methyldimethoxy(l-phenylethenoxy)silane;methyldimethoxy-2(1-carboethoxypropenoxy)silane;methylmethoxydi-N-methylaminosilane; vinyldimethoxymethylaminosilane;tetra-N,N-diethylaminosilane; methyldimethoxymethylaminosilane;methyltricyclohexylaminosilane; methyldimethoxyethylaminosilane;dimethyldi-N,N-dimethylaminosilane; methyldimethoxyisopropylaminosilane;dimethyldi-N,N-diethylaminosilane;ethyldimethoxy(N-ethylpropionamido)silane;methyldimethoxy(N-methylacetamido)silane;methyltris(N-methylacetamido)silane;ethyldimethoxy(N-methylacetamido)silane;methyltris(N-methylbenzamido)silane;methylmethoxybis(N-methylacetamido)silane;methyldimethoxy(caprolactamo)silane;trimethoxy(N-methylacetamido)silane;methyldimethoxyethylacetimidatosilane;methyldimethoxypropylacetimidatosilane; methyldimethoxy(N,N′,N′-trimethylureido)silane;methyldimethoxy(N-allyl-N′,N′-dimethylureido)silane;methyldimethoxy(N-phenyl-N′,N′-dimethylureido)silane;methyldimethoxyisocyanatosilane; dimethoxydiisocyanatosilane;methyldimethoxythioisocyanatosilane;methylmethoxydithioisocyanatosilane, or combinations of two or morethereof. In one embodiment, the crosslinker may be present in an amountfrom about 1 to about 10 wt. % of the composition or from about 0.1 toabout 10 pt. wt. per 100 pt. wt. of the polymer component (A). Inanother embodiment, the crosslinker may be present in an amount fromabout 0.1 to about 5 pt. wt. per 100 pt. wt. of the polymer component(A). In still another embodiment, the crosslinker may be present in anamount from about 0.5 to about 3 pt. wt. per 100 pt. wt. of the polymercomponent (A). Here as elsewhere in the specification and claims,numerical values may be combined to form new or undisclosed ranges.

Additional alkoxysilanes in an amount greater than 0.1 wt. % ofcomponent and (A) that are not consumed by the reaction between theprepolymer Z′—X—Z′ and which comprise additional functional groupsselected from R⁴ can also work as an adhesion promoter and are definedand counted under component (D).

The composition furthers include an adhesion promoter component (D) thatis different to component (A₁) or (B₁). In one embodiment, the adhesionpromoter (D) may be an organofunctional silane comprising the group R⁴,e.g., aminosilanes, and other silanes that are not identical to thesilanes of component (C), or are present in an amount which exceeds theamount of silanes necessary for endcapping the polymer (A). The amountof non-reacted silane (B₁) or (D₁) in the reaction for making (A) can bedefined in that after the endcapping reaction the free silanes areevaporated at a higher temperature up to 200° C. and vacuum up to 1 mbarto be more than 0.1 wt. % of (A).

In one embodiment, the composition comprises an adhesion promoter (D)comprising a group R⁴ as described by the general formula (7a):R⁴ _(e)R¹ _(d)Si(OR³)_(4-d-e)  (7a)where R⁴ is E-(CR⁵ ₂)_(f)—W—(CH₂)_(f)—; R¹ is as described above; d is0, 1 or 2; e=1, 2 or 3; d+e=1 to 2; and f is 0 to 8, and may beidentical or different.

Non-limiting examples of suitable compounds include:E¹-(CR⁵ ₂)_(f)—W—(CH₂)_(f)SiR¹ _(d)(OR³)_(3-d)  (7c), or (7d)E²-[(CR⁵ ₂)_(f)—W—(CH₂)_(f)SiR¹ _(d)(OR³)_(3-d)]_(p)  (7b) or (7f)where p=2-3.

The group E may be selected from either a group E¹ or E². E¹ may beselected from a monovalent group comprising amine, —NH₂, —NHR,—(NHC₂H₅)₁₋₁₀NHR, NHC₆H₅ halogen, pseudohalogen, unsaturated aliphaticgroup with up to 14 carbon atoms, epoxy-group-containing aliphatic groupwith up to 14 carbon atoms, cyanurate-containing group, and anisocyanurate-containing group.

E² may be selected from a group comprising of a di- or multivalent groupconsisting of amine, polyamine, isocyanurate-containing and anisocyanurate-containing group, sulfide, sulfate, phosphate, phosphiteand a polyorganosiloxane group, which can contain R⁴ and OR³ groups; Wis selected from the group consisting of a single bond, a heteroatomicgroup selected from —COO—, —O—, epoxy, —S—, —CONH—, —HN—CO—NH— units; R⁵is selected from hydrogen and R as defined above, R¹ may be identical ordifferent as defined above, R³ is selected from the group, whichconsists of C₁-C₈-alkoxy, such as methoxy, ethoxy, C₃-C₁₂-alkoxyalkyl,C₂-C₂₂-alkylcarboxy and C₄-C₁₀₀ polyalkylene oxide may be identical ordifferent.

Non-limiting examples of component (D) include:

wherein R and d are as defined above.

An exemplary group of adhesion promoters are selected from the groupwhich consists of amino group-containing silane coupling agents. Theamino group-containing silane adhesion promoter agent (D) is a compoundhaving a group containing a silicon atom bonded to a hydrolyzable group(hereinafter referred to as a hydrolyzable group attached to the siliconatom) and an amino group. Specific examples thereof include the samesilyl groups with hydrolyzable groups described above. Among thesegroups, the methoxy group and ethoxy group are particularly suitable.The number of the hydrolyzable groups may be 2 or more, and particularlysuitable are compounds having 3 or more hydrolyzable groups.

Examples of other suitable adhesion promoter (D) include, but are notlimited to N-(2-amino ethyl)aminopropyltrimethoxysilane,γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane,bis(γ-trimethoxysilylpropyl)amine,N-phenyl-γ-aminopropyltrimethoxysilane,triaminofunctionaltrimethoxysilane, γ-aminopropylmethyldimethoxysilane,γ-aminopropylmethyldiethoxysilane, methacryloxypropyltrimethoxysilane,methylaminopropyltrimethoxysilane,γ-glycidoxypropylethyldimethoxysilane,γ-glycidoxypropyltrimethoxysilane, γ-glycidoxyethyltrimethoxysilane,γ-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,beta-(3,4-epoxycyclohexyl)ethylmethyl-dimethoxysilane,epoxylimonyltrimethoxysilane, isocyanatopropyltriethoxysilane,isocyanatopropyltrimethoxysilane, isocyanatopropylmethyldimethoxysilane,beta-cyano-ethyl-trimethoxysilane, γ-acryloxypropyl-trimethoxy-silane,γ-methacryloxypropyl-methyldimethoxysilane,α,Ω-bis-(aminoalkyl-diethoxysilyl)-polydimethylsiloxanes (Pn=1-7),α,Ω-bis-(aminoalkyl-diethoxysilyl)-octa-methyltetrasiloxane,4-amino-3,3-dimethyl-butyl-trimethoxysilane, andN-ethyl-3-tri-methoxy-silyl-2-methylpropanamine,3-(diethyl-aminopropyl)-trimethoxysilane combinations of two or morethereof, and the like. Particularly suitable adhesion promoters includebis(alkyltrialkoxysilyl)amines and tris(alkyltrialkoxysilyl)aminesincluding, but not limited to, bis(3-propyltrimethoxysilyl)amine andtris(3-propyltrimethoxysilyl)amine.

Also, it is possible to use derivatives obtained by modifying them, forexample, amino-modified silyl polymer, silylated amino polymer,unsaturated aminosilane complex, phenylamino long-chain alkyl silane andaminosilylated silicone. These amino group-containing silane couplingagents may be used alone, or two or more kinds of them may be used incombination.

The curable compositions of the present disclosure may further comprisean alkoxysilane or blend of alkoxysilanes as an adhesion promoter (D).The adhesion promoter may be a combination blend ofN-2-aminoethyl-3-aminopropyltrimethoxysilane and1,3,5-tris(trimethoxy-silylpropyl)isocyanurate and others.

The adhesion promoter (D) may be present in an amount of from about 0.1to about 5.0 pt. wt. based on 100 parts of the polymer component (A). Inone embodiment, the adhesion promoter may be present in an amount offrom about 0.15 to about 2.0 pt. wt. In another embodiment, the adhesionpromoter may be present in an amount of from about 0.5 to about 1.5parts per weight (pt. wt.) of the polymer component (A) This defines theamount of (D) in composition of (A) wherein the content of free silanescoming from the endcapping of polymer (A) is smaller than 0.1 wt. %.

The present compositions may further include a filler component (E). Thefiller component(s) (E) may have different functions, such as to be usedas reinforcing or semi-reinforcing filler, i.e., to achieve highertensile strength after curing having in addition the ability to increasethe viscosity establish pseudoplasticity/shear thinning, and thixotropicbehavior as well as non-reinforcing fillers acting mainly as a volumeextender. The reinforcing fillers are characterized by having a specificsurface area of more than 50 m²/g related BET-surface, whereby thesemi-reinforcing fillers have a specific surface area in the range of10-50 m²/g. So-called extending fillers have preferably a specificsurface of less than 10 m²/g according to the BET-method and an averageparticle diameter below 100 um. In one embodiment, the semi-reinforcingfiller is a calcium carbonate filler, a silica filler, or a mixturethereof. Examples of suitable reinforcing fillers include, but are notlimited to fumed silicas or precipitated silica, which can be partiallyor completely treated with organosilanes or siloxanes to make them lesshydrophilic and decrease the water content or control the viscosity andstorage stability of the composition. These fillers are namedhydrophobic fillers. Tradenames of representative filler componentsinclude AEROSIL™, HDK™, and CAB-O-SIL™.

Examples of suitable extending fillers include, but are not limited to,ground silicas (CELITE), precipitated and colloidal calcium carbonates(which are optionally treated with compounds such as stearate or stearicacid); reinforcing silicas such as fumed silicas, precipitated silicas,silica gels and hydrophobized silicas and silica gels; crushed andground quartz, cristobalite, alumina, aluminum hydroxide, titaniumdioxide, zinc oxide, diatomaceous earth, iron oxide, carbon black,powdered thermoplastics such as acrylonitrile, polyethylene,polypropylene, polytetrafluoroethylene and graphite or clays such askaolin, bentonite or montmorillonite (treated/untreated), and the like.

The type and amount of filler added depends upon the desired physicalproperties for the cured silicone/non-silicone composition. As such, thefiller may be a single species or a mixture of two or more species. Theextending fillers can be present from about 0 to about 300 wt. % of thecomposition related to 100 parts of component (A). The reinforcingfillers can be present from about 5 to about 60 wt. of the compositionrelated to 100 parts of component (A₁, preferably 5 to 30 wt. %.

The inventive compositions may further comprise an acidic compound (F),which, in conjunction with the adhesion promoter and catalyst, has beenfound to accelerate curing (as compared to curing in the absence of suchcompounds). The component (F) may be present in an amount of from about0.01 to about 5 wt. % of the composition. In another embodiment 0.01 toabout 8 pt. wt. per 100 pt. wt. of component (A) are used, morepreferably 0.02 to 3 pt. wt. per 100 pt. wt. of component (A) and mostpreferably 0.02 to 1 pt. wt. per 100 pt. wt. of component (A) are used.

The acidic compounds (F) may be chosen from various phosphate esters,phosphonates, phosphites, phosphines, sulfites, pseudohalogenides,branched alkyl carboxylic acids, combinations of two or more thereof,and the like. Without being bound to any particular theory, the acidiccompounds (F) may, in one embodiment, be useful as stabilizers in orderto ensure a longer storage time when sealed in a cartridge before use incontact with ambient air. Especially alkoxy-terminated polysiloxanes canlose the ability to cure after storage in a cartridge and show e.g.decreased hardness under curing conditions. It may, therefore be usefulto add compounds of the formula (8a), which can extend storage time orability to cure over months:O═P(OR⁷)_(3-r)(OH)_(r)  (8a)whereby r is 0, 1 or 2, and R⁷ is selected from the group a linear orbranched and optionally substituted C₁-C₃₀-alkyl groups, linear orbranched, C₅-C₁₄-cycloalkyl groups, C₆-C₁₄-aryl groups, C₆-C₃₁ alkylarylgroups, linear or branched C₂-C₃₀-alkenyl groups or linear or branchedC₁-C₃₀-alkoxy-alkyl groups, C₄-C₃₀₀-polyalkenylene oxide groups(polyethers), such as MARLOPHOR N5 acid, triorganylsilyl- anddiorganyl(C₁-C₈)-alkoxysilyl groups. The phosphates can include alsomixtures of primary and secondary esters. Non-limiting examples ofsuitable phosphonates include 1-hydroxyethane-(1,1-diphosphonate)(HEDP), aminotrimethylene phosphonate (ATMP),nitrolotris(methylphosphonate) (NTMP),diethylenetriamine-pentakismethylene phosphonate (DTPMP),1,2-diaminoethane-tetrakismethylene phosphonate (EDTMP), andphosphonobutanetricarbonate (PBTC).

In another embodiment, a compound of the formula O═P(OR⁷)_(2-t)(OH)_(t)may be added where t is 1 or 2, and R⁷ is as defined above or di- ormulitvalent hydrocarbons with one or more amino group.

Another type are phosphonic acid compounds of the formula O═PR⁷(OH)₂such as alkyl phosphonic acids preferably hexyl or octyl phosphonicacid.

In one embodiment, the acidic compound may be chosen from a mono esterof a phosphate; a phosphonate of the formula (R³O)PO(OH)₂, (R³O)P(OH)₂,or R³P(O)(OH)₂ where R³ is a C₁-C₈-alkyl, a C₂-C₂₀-alkoxyalkyl, phenyl,a C₇-C₁₂-alkylaryl, a poly(C₂-C₄-alkylene)oxide ester or its mixtureswith diesters.

In another embodiment, the acidic compound is a branched alkylC₄-C₃₀-alkyl carboxylic acids, including C₅-C₁₉ acids with alphatertiary carbon, or a combination of two or more thereof. Examples ofsuch suitable compounds include, but are not limited to, versatic acid,lauric acid, and stearic acid. In one embodiment, the acidic compoundmay be a mixture comprising branched alkyl carboxylic acids. In oneembodiment, the acidic compound is a mixture of mainly tertiaryaliphatic C₁₀-carboxylic acids.

Applicants have found that the combination of catalyst of the currentdisclosure, namely metal amidine complexes in combination withcarboxylate salts of various amines and an acidic compound may provide acurable composition that provides a cured polymer exhibiting a tack-freetime, hardness, and/or cure time comparable to compositions made usingtin catalysts, but that provide better adhesion compared to materialsmade using tin catalysts.

Generally, the acidic component (F) is added in a molar ratio of lessthan 1 with respect to catalyst (B). In embodiments, the acidiccomponent (F) is added in a molar ratio of (F):(C) of 1:10 to 1:4.

The curable composition may also include auxiliary substances (G) suchas plastizers, pigments, stabilizers, anti-microbial or fungicides,biocides and/or solvents. Preferred plastizers for reactivepolyorganosiloxanes (A) are selected from the group ofpolyorganosiloxanes having chain length of 10-300 siloxy units.Preferred are trimethylsilyl terminated polydimethylsiloxanes having aviscosity of 100-1000 mPas at 25° C. The choice of optional solvents(dispersion media or extenders) may have a role in assuring uniformdispersion of the catalyst, thereby altering curing speed. Such solventsinclude polar and non-polar solvents such as toluene, hexane,chloroform, methanol, ethanol, isopropyl alcohol, acetone, methylethylketone, dimethylformamide (DMF), dimethyl sulfoxide (DMSO). Water can bean additional component (G) to accelerate fast curing 2 partcompositions RTV 2-K, whereby the water can be in one part of the 2compositions. Particularly suitable non-polar solvents include, but arenot limited to, toluene, hexane and the like if the solvents shouldevaporate after cure and application. In another embodiment, thesolvents include high boiling hydrocarbons such as alkylbenzenes,phthalic acid esters, arylsulfonic acid esters, trialkyl- ortriarylphosphate esters, which have a low vapor pressure and can extendthe volume providing lower costs. Examples cited by reference may bethose of U.S. Pat. Nos. 6,599,633; 4,312,801. The solvent can be presentin an amount of from about 20 to about 99 wt. % of the catalystcomposition.

In one embodiment, a composition in accordance with the presentdisclosure comprises: 100 pt. wt. polymer component (A); about 0.1 toabout 10 pt. wt. crosslinker component (C); about 0.01 to about 7 pt.wt. catalyst component (B); about 0.1 to about 5, in one embodiment0.15-1 pt. wt., of an adhesion promoter component (D); about 0 to about300 pt. wt. filler component (E); about 0.01 to about 7 pt. wt. ofacidic compound (F); optionally 0 to about 15 pt. wt. component (G₁),where the pt. wt. of components (B)-(G) are each based on 100 parts ofthe polymer component (A). In one embodiment the composition comprisesthe component (F) in an amount of from about 0.01 to about 1 pt. wt. per100 pt. wt. of component (A). In still another embodiment, thecomposition comprises the catalyst (C₁) in an amount of from about 0.1to about 0.8 pt. wt. per 100 wt. pt of component (A).

It will be appreciated that the curable compositions may be provided aseither a one-part composition or a two-part composition. A one-partcomposition refers to a composition comprising a mixture of the variouscomponents described above. A two-part composition may comprise a firstportion and a second portion that are separately stored and subsequentlymixed together just prior to application for curing. In one embodiment,a two-part composition comprises a first portion (X₁) comprising apolymer component (A) and a crosslinker component (C), and a secondportion (X₂) comprising the catalyst component (B) comprising a catalystof the current disclosure, namely metal amidine complexes in combinationwith carboxylate salts of various amines The first and second portionsmay include other components (F) and/or (G) as may be desired for aparticular purpose or intended use. For example, in one embodiment, thefirst portion (X₁) may optionally comprise an adhesion promoter (D)and/or a filler (E), and the second portion (X₂) may optionally compriseauxiliary substances (G), a cure rate modifying component (F), and water(G).

In one embodiment, a two-part composition comprises (i) a first portioncomprising the polymer component (A), optionally the filler component(E), and optionally the acidic compound (F); and (ii) a second portioncomprising the crosslinker (C), the catalyst component (B), the adhesivepromoter (D), and the acidic compound (F), where portions (i) and (ii)are stored separately until applied for curing by mixing of thecomponents (i) and (ii).

An exemplary “Two-Part” composition comprises: a first portion (i)comprising 100 pt. wt of component (A) and 0 to 70 pt. wt of component(E); and a second portion (ii) comprising 0.1 to 5 pt. wt of at leastone crosslinker (C); 0.01 to 2 pt. wt. of a catalyst (B); 0.1 to 2 p.wt. of an adhesion promoter (D); and 0.02 to 1 pt. wt. component (F).

The curable compositions may be used in a wide range of applicationsincluding as materials for sealing, mold making, adhesives, coatings insanitary rooms, glazing, prototyping, joint seal between differentmaterials, e.g., sealants between ceramic or mineral surfaces andthermoplastics, paper release, impregnation, and the like. A curablecomposition in accordance with the present disclosure comprising acatalyst of the current disclosure, namely metal amidine complexes incombination with carboxylate salts of various amines may be suitable fora wide variety of applications such as, for example, a general purposeand industrial sealant, potting compound, caulk, adhesive or coating forconstruction use, insulated glass (IG), structural glazing (SSG), whereglass sheets are fixed and sealed in metal frame; caulks, adhesives formetal plates, car bodies, vehicles, electronic devices and the like.Furthermore, the present composition may be used either as a one-partRTV-1K or as a two-part room temperature vulcanizing (RTV-2K)formulation which can adhere onto broad variety of metal, mineral,ceramic, rubber or plastic surfaces.

The following examples are submitted for the purpose of furtherillustrating the nature of the present disclosure and should not beconstrued as a limitation on the scope thereof.

EXAMPLES

Metal Amidine Complex Preparation

[Metal(Amidine)₂(Ligand)_(x)] of this disclosure: To a mixture ofamidine (2.0 moles) and metal carboxylate, or acetylacetonate (1 mole)was added methanol to make a 50% solution. The mixture was held at 50°C. for 2 hours or until it became a clear solution. The solution wasfiltered and dried. The example metal amidine catalystsMetal(Amidine)₂(Ligand)_(x) are listed in TABLE 1. “x” is the oxidationstate of the metal.

TABLE 1 Example Metal Amidine Complex Physical Form 1Zn(DBN*)₂(acetate)₂ white powder 2 Zn(DBN*)₂(formate)₂ white powder 3Zn(DBN*)₂(2-ethylhexanoate)₂ clear liquid 4 Zn(DBN*)₂(neodecanoate)₂clear liquid 5 Zn(DBU*)₂(acetate)₂ white powder 6 Zn(DBU*)₂(formate)₂white powder 7 Zn(DBU*)₂(2-ethylhexanoate)₂ clear liquid 8Zn(DBU*)₂(neodecanoate)₂ clear liquid 9 Zn(1-methylimidazole)₂(acetate)₂white powder 10 Zn(1-methylimidazole)₂(formate)₂ white powder 11Zn(1-methylimidazole)₂(2-ethylhexanoate)₂ clear liquid 12Zn(1-methylimidazole)₂(neodecanoate)₂ clear liquid 13Zn(1,2-dimethylimidazole)₂(acetate)₂ white powder 14Zn(1,2-dimethylimidazole)₂(formate)₂ white powder 15Zn(1,2-dimethylimidazole)₂(2-ethylhexanoate)₂ clear liquid 16Zn(1,2-dimethylimidazole)₂(neodecanoate)₂ clear liquid 17Zn(1-butylimidazole)₂(acetate)₂ white powder 18Zn(1-butylimidazole)₂(formate)₂ white powder 19Zn(1-butylimidazole)₂(2-ethylhexanoate)₂ clear liquid 20Zn(1-butylimidazole)₂(neodecanoate)₂ clear liquid 21Zn(imidazole)₂(acetate)₂ white powder 22 Zn(imidazole)₂(formate)₂ whitepowder 23 Zn(imidazole)₂(2-ethylhexanoate)₂ clear liquid 24Zn(imidazole)₂(neodecanoate)₂ clear liquid 25Zn(tetramethylguanidine)₂(acetate)₂ white powder 26Zn(tetramethylguanidine)₂(formate)₂ white powder 27Zn(tetramethylguanidine)₂(2-ethylhexanoate)₂ clear liquid 28Zn(tetramethylguanidine)₂(neodecanoate)₂ clear liquid 29Zn(1,3-diphenylguanidine)₂(acetate)₂ white powder 30Zn(1,3-diphenylguanidine)₂(formate)₂ white powder 31Zn(1,3-diphenylguanidine)₂(2-ethylhexanoate)₂ clear liquid 32Zn(1,3-diphenylguanidine)₂(neodecanoate)₂ clear liquid 33Zn(4,4-dimethyl-2-imidazoline)₂(acetate)₂ white powder 34Zn(4,4-dimethyl-2-imidazoline)₂(formate)₂ white powder 35Zn(4,4-dimethyl-2-imidazoline)₂(2-ethylhexanoate)₂ clear liquid 36Zn(4,4-dimethyl-2-imidazoline)₂(neodecanoate)₂ clear liquid 37Zn(MACKAZOLINE T*)₂(acetate)₂ brown liquid 38 Zn(MACKAZOLINET*)₂(formate)₂ brown liquid 39 Zn(MACKAZOLINE T*)₂(2-ethylhexanoate)₂brown liquid 40 Zn(MACKAZOLINE T*)₂(neodecanoate)₂ brown liquid 41Zn(Lindax-1*)₂(acetate)₂ brown liquid 42 Zn(Lindax-1*)₂(formate)₂ brownliquid 43 Zn(Lindax-1*)₂(2-ethylhexanoate)₂ brown liquid 44Zn(Lindax-1*)₂(neodecanoate)₂ brown liquid 45 Zn(1-phenylguanidine)₂(acetate)₂ white powder 46 Zn(1-phenyl guanidine)₂(formate)₂white powder 47 Zn(1-phenyl guanidine)₂(2-ethylhexanoate)₂ clear liquid48 Zn(1-phenyl guanidine)₂(neodecanoate)₂ clear liquid 49Zn(1-methylimidazole)₂(acac)₂ white powder 50Bi(1-methylimidazole)₂(acetate)₃ white powder 51Ca(1-methylimidazole)₂(acetate)₂ white powder 52Cd(1-methylimidazole)₂(acetate)₂ white powder 53La(1-methylimidazole)₂(acetate)₃ white powder 54Zr(1-methylimidazole)₂(acetate)x(hydroxide)y x + y = 4 white powder 55Hf(1-methylimidazole)₂(acac)₄ yellow liquid *DBN:1,5-Diazabicyclo[4.3.0] non-5-ene DBU:1,8-Diazabicyclo [5.4.0] undec-7-ene Amidines,Zinc Acetate Anhydrous, and Zinc Acetylacetonate [Zn(acac)₂] supplied byAldrich. Zinc Formate Anhydrous and Zinc 2-Ethylhexanoate supplied byAlfa Aesar. MACKAZOLINE T ™ supplied by McIntyre Group is tall oilhydroxyethyl imidazoline. Lindax-1 ™ supplied by Lindau Chemicals Inc.is 1-(2-hydroxypropyl)imidazoleAmine/Carboxylic Acid Salt Preparation

An amine/carboxylic acid salt according to this disclosure: One mole ofan amine was added into a flask. Three moles of an acid were introducedto a flask slowly under agitation. The mixture was held at 50° C. for 2hours. The solution was filtered. The example amine/carboxylic acidsalts are listed in TABLE 2.

TABLE 2 Example Amine/Carboxylic Acid Salt 1 DBN/2-ethylhexanoic acid 2DBN/neodecanoic acid 3 DBN/naphthenic acid 4 DBU/2-ethylhexanoic acid 5DBU/neodecanoic acid 6 DBU/naphthenic acid 71-methylimidazole/2-ethylhexanoic acid 8 1-methylimidazole/neodecanoicacid 9 1-methylimidazole/naphthenic acid 101,2-dimethylimidazole/2-ethylhexanoic acid 111,2-dimethylimidazole/neodecanoic acid 121,2-dimethylimidazole/naphthenic acid 131-butylimidazole/2-ethylhexanoic acid 14 1-butylimidazole/neodecanoicacid 15 1-butylimidazole/naphthenic acid 16 imidazole/2-ethylhexanoicacid 17 imidazole/neodecanoic acid 18 imidazole/naphthenic acid 19tetramethylguanidine/2-ethylhexanoic acid 20tetramethylguanidine/neodecanoic acid 21 tetramethylguanidine/naphthenicacid 22 1,3-diphenylguanidine/2-ethylhexanoic acid 231,3-diphenylguanidine/neodecanoic acid 241,3-diphenylguanidine/naphthenic acid 254,4-dimethyl-2-imidazoline/2-ethylhexanoic acid 264,4-dimethyl-2-imidazoline/neodecanoic acid 274,4-dimethyl-2-imidazoline/naphthenic acid 283-(diethylamino)propylamine (DMAPA)/2-ethylhexanoic acid 293-(diethylamino)propylamine (DMAPA)/neodecanoic acid 303-(diethylamino)propylamine (DMAPA)/naphthenic acid 311-dimethylamino-2-propanol (DMPA)/2-ethylhexanoic acid 321-dimethylamino-2-propanol (DMPA)/neodecanoic acid 331-dimethylamino-2-propanol (DMPA)/naphthenic acid 342-(dimethylamino)ethanol (DMEA)/2-ethylhexanoic acid 352-(dimethylamino)ethanol (DMEA)/neodecanoic acid 362-(dimethylamino)ethanol (DMEA)/naphthenic acid 37 1-phenylguanidine/2-ethylhexanoic acid 38 1-phenyl guanidine/neodecanoic acid 391-phenyl guanidine/naphthenic acidCatalyst Preparation

A catalyst according to this disclosure: A metal amidine complex (50% byweight) listed in TABLE 1 was mixed with an amine/carboxylic acid salt(50% by weight) listed in TABLE 2 for 2 hours. The solution wasfiltered. The example catalysts are listed in TABLE 3.

TABLE 3 Example Catalyst 1 Zn(DBN)₂(2-ethylhexanoate)₂ +DBN/2-ethylhexanoic acid 2 Zn(DBN)₂(neodecanoate)₂ + DBN/neodecanoicacid 3 Zn(DBN)₂(neodecanoate)₂ + DBN/naphthenic acid 4Zn(DBU)₂(2-ethylhexanoate)₂ + DBU/2-ethylhexanoic acid 5Zn(DBU)₂(neodecanoate)₂ + DBU DBU/neodecanoic acid 6Zn(DBU)₂(neodecanoate)₂ + DBU/naphthenic acid 7Zn(1-methylimidazole)₂(2-ethylhexanoate)₂ +1-methylimidazole/2-ethylhexanoic acid 8Zn(1-methylimidazole)₂(neodecanoate)₂ + 1-methylimidazole/neodecanoicacid 9 Zn(1-methylimidazole)₂(neodecanoate)₂ +1-methylimidazole/naphthenic acid 10Zn(1,2-dimethylimidazole)₂(2-ethylhexanoate)₂ +1,2-dimethylimidazole/2-ethylhexanoic acid 11Zn(1,2-dimethylimidazole)₂(neodecanoate)₂ +1,2-dimethylimidazole/neodecanoic acid 12Zn(1,2-dimethylimidazole)₂(neodecanoate)₂ +1,2-dimethylimidazole)/naphthenic acid 13Zn(1-butylimidazole)₂(2-ethylhexanoate)₂ +1-butylimidazole/2-ethylhexanoic acid 14Zn(1-butylimidazole)₂(neodecanoate)₂ + 1-butylimidazole/neodecanoic acid15 Zn(1-butylimidazole)₂(neodecanoate)₂ + 1-butylimidazole/naphthenicacid 16 Zn(imidazole)₂(2-ethylhexanoate)₂ + imidazole/2-ethylhexanoicacid 17 Zn(imidazole)₂(neodecanoate)₂ + imidazole/neodecanoic acid 18Zn(imidazole)₂(neodecanoate)₂ + imidazole/naphthenic acid 19Zn(tetramethylguanidine)₂(2-ethylhexanoate)₂ +tetramethylguanidine/2-ethylhexanoic acid 20Zn(tetramethylguanidine)₂(neodecanoate)₂ +tetramethylguanidine/neodecanoic acid 21Zn(tetramethylguanidine)₂(neodecanoate)₂ +tetramethylguanidine/naphthenic acid 22Zn(1,3-diphenylguanidine)₂(2-ethylhexanoate)₂ +1,3-diphenylguanidine/2-ethylhexanoic acid 23Zn(1,3-diphenylguanidine)₂(neodecanoate)₂ +1,3-diphenylguanidine/neodecanoic acid 24Zn(1,3-diphenylguanidine)₂(neodecanoate)₂ +1,3-diphenylguanidine/naphthenic acid 25Zn(4,4-dimethyl-2-imidazoline)₂(2-ethylhexanoate)₂ +4,4-dimethy1-2-imidazoline/2- ethylhexanoic acid 26Zn(4,4-dimethyl-2-imidazoline)₂(neodecanoate)₂ +4,4-dimethyl-2-imidazoline/neodecanoic acid 27Zn(4,4-dimethyl-2-imidazoline)₂(neodecanoate)₂ +4,4-dimethyl-2-imidazoline/naphthenic acid 28Zn(1-methylimidazole)₂(2-ethylhexanoate)₂ + 3-(diethylamino)propylamine(DMAPA)/2- ethylhexanoic acid 29Zn(tetramethylguanidine)₂(neodecanoate)₂ + 3-(diethylamino)propylamine(DMAPA)/neodecanoic acid 30 Zn(DBU)2(neodecanoate)₂ +3-(diethylamino)propylamine (DMAPA)/neodecanoic acid 31Zn(1-methylimidazole)₂(2-ethylhexanoate)₂ + 1-dimethylamino-2-propanol(DMPA)/2- ethylhexanoic acid 32Zn(tetramethylguanidine)₂(neodecanoate)₂ + 1-dimethylamino-2-propanol(DMPA)/neodecanoic acid 33 Zn(DBU)2(neodecanoate)₂ +1-dimethylamino-2-propanol (DMPA)/neodecanoic acid 34Zn(1-methylimidazole)₂(2-ethylhexanoate)₂ + 2-(dimethylamino)ethanol(DMEA)/2- ethylhexanoic acid 35Zn(tetramethylguanidine)₂(neodecanoate)₂ + 2-(dimethylamino)ethanol(DMEA)/neodecanoic acid 36 Zn(DBU)2(neodecanoate)₂ +2-(dimethylamino)ethanol (DMEA)/neodecanoic acid 37Zn(1-methylimidazole)₂(2-ethylhexanoate)₂ + 1-phenylguanidine/2-ethylhexanoic acid 38Zn(tetramethylguanidine)₂(neodecanoate)₂ + 1-phenylguanidine/neodecanoic acid 39 Zn(DBU)2(neodecanoate)₂ + 1-phenylguanidine/neodecanoic acidUncatalyzed Sealant Preparation

An uncatalyzed sealant of this disclosure: Uncatalyzed sealants wereprepared according to the procedures listed in TABLE 4. Silane polymersof this disclosure included dimethoxysilane terminated polyester (DMS),trimethoxysilane terminated polyester (TMS), and diethoxysilaneterminated polyether urea (DES). Uncatalyzed sealants were packaged incartridge tubes.

TABLE 4 Ingredients Description Eastman 168 Dioctyl terephthalateplasticizer HiPflex 100 3 micron treated ground calcium carbonate UltraPflex 0.07 micron treated precipitated calcium carbonate KRT 12-C TiO2Titanium dioxide Ethanox 310 Antioxidant Tinuvin 770 HALS Mix untiluniform, scrape Mix/vac 1 hr @ 200+° F., Check Moisture Continue mix/vacuntil < 0.08%, then add: p-TSI Monoisocyanate (dessication) Mix 5 min w/N₂, scrape quickly, Mix/vac 15 min, then add: Silane Polymer Mix/vac 15min, then add: Aerosil R202 Fumed silica Mix until uniform, scrapeMix/vac 15 minCure Studies in a Dimethoxysilane Terminated Polyester System

Sealant Preparation: Dispense 30 grams of the uncatalyzed sealant (DMS)described in TABLE 5 from cartridge tube into speed mixer containerusing a caulk gun. Add catalyst and mix on the speed mixer using Program3 (30 seconds @ 1500 rpm then 2 minutes @ 2200 rpm). Use adjustabledoctor blade to apply 3 mm of the blend onto a paper substrate. Monitorcure time by applying a folded 1″×2″ strip of paper onto the castingsurface and measuring tack after applying weights onto the folded paperstrips. Gauge the degree of cure based on the time needed for thecasting to be tack free after application of 20, 50, 100, 200, and 500gram weights. Allow the weights to remain on the paper for approximately5 seconds before lifting the paper strip. Touch dry time was determinedby passing the weight of 20 grams and through dry time was determined bypassing the weight of 500 grams. The formulation is tabulated in TABLE5. The catalyst levels of dioctyltin diacac (Control) and disclosurecatalysts were 0.6% and 2.0% based on total formulation, respectively.

TABLE 5 Ingredient % by weight Eastman 168 23.4 HiPflex 100 27.7 UltraPflex 22.2 KRT 12-C TiO2 3.3 Ethanox 310 0.3 Tinuvin 770 0.3 p-TSI 0.8Dimethoxysilane (DMS) 20.5 Aerosil R202 1.4 Dioctyltin Diacac (Control)0.6 Disclosure Catalyst 2.0

TABLE 6 Touch Through Exam- % Dry Dry ples Catalysts Catalyst HoursHours 1 Dioctyltin Diacac (Control) 0.6 1.5 4.0 2Zn(1-methylimidazole)₂(2- 2.0 3.0 7.5 ethylhexanoate)₂ + 3-(diethylamino)propylamine (DMAPA)/2-ethylhexanoic acid 3Zn(tetramethylguanidine)₂ 2.0 1.5 4.5 (neodecanoate)₂ + 3-(diethylamino)propylamine (DMAPA)/neodecanoic acid 4Zn(DBU)₂(neodecanoate)₂ + 3- 2.0 1.5 4.0 (diethylamino)propylamine(DMAPA)/neodecanoic acid 5 Zn(1-methylimidazole)₂(2- 2.0 3.0 8.5ethylhexanoate)₂ + 1- dimethylamino-2-propanol (DMPA)/2-ethylhexanoicacid 6 Zn(tetramethylguanidine)₂ 2.0 2.5 7.0 (neodecanoate)₂ +1-dimethylamino- 2-propanol (DMPA)/neodecanoic acid 7Zn(DBU)2(neodecanoate)₂ + 1- 2.0 2.5 6.5 dimethylamino-2-propanol(DMPA)/neodecanoic acid 8 Zn(1-methylimidazole)₂(2- 2.0 3.0 7.5ethylhexanoate)₂ + 2- (dimethylamino)ethanol (DMEA)/2- ethylhexanoicacid 9 Zn(tetramethylguanidine)₂ 2.0 2.5 7.0 (neodecanoate)₂ +2-(dimethylamino) ethanol (DMEA)/neodecanoic acid 10Zn(DBU)2(neodecanoate)₂ + 2- 2.0 2.5 8.0 (dimethylamino)ethanol(DMEA)/neodecanoic acid

Examples 1-10 in TABLE 6 demonstrate that the mixtures of zinc amidinecomplexes (50% by weight) and amine/carboxylic acid salts (50% byweight) are effective catalysts for a dimethoxysilane terminatedpolyester (DMS) based sealant.

Cure Studies in a Trimethoxysilane Terminated Polyester System

Sealant Preparation: Dispense 30 grams of the uncatalyzed sealant (TMS)described in TABLE 7 from cartridge tube into speed mixer containerusing a caulk gun. Add catalyst and mix on the speed mixer using Program3 (30 seconds @ 1500 rpm then 2 minutes @ 2200 rpm). Use adjustabledoctor blade to apply 3 mm of the blend onto a paper substrate. Monitorcure time by applying a folded 1″×2″ strip of paper onto the castingsurface and measuring tack after applying weights onto the folded paperstrips. Gauge the degree of cure based on the time needed for thecasting to be tack free after application of 20, 50, 100, 200, and 500gram weights. Allow the weights to remain on the paper for approximately5 seconds before lifting the paper strip. Touch dry time was determinedby passing the weight of 20 grams and through dry time was determined bypassing the weight of 500 grams. The formulation is tabulated in TABLE5. The catalyst levels of dioctyltin diacac (Control) and disclosurecatalysts were 0.6% and 2.0% based on total formulation, respectively.

TABLE 7 Ingredient % by weight Eastman 168 23.4 HiPflex 100 27.7 UltraPflex 22.2 KRT 12-C TiO2 3.3 Ethanox 310 0.3 Tinuvin 770 0.3 p-TSI 0.8Trimethoxysilane (TMS) 20.5 Aerosil R202 1.4 Dioctyltin Diacac (Control)0.6 Disclosure Catalyst 2.0

TABLE 8 Touch Through % Dry Dry Examples Catalysts Catalyst Hours Hours11 Dioctyltin Diacac (Control) 0.6 1.0 2.0 12 Zn(1-methylimidazole)₂(2-2.0 3.0 7.0 ethylhexanoate)₂ + 3- (diethylamino)propylamine(DMAPA)/2-ethylhexanoic acid 13 Zn(tetramethylguanidine)₂ 2.0 1.5 3.0(neodecanoate)₂ + 3- (diethylamino)propylamine (DMAPA)/neodecanoic acid14 Zn(DBU)2(neodecanoate)₂ + 3- 2.0 1.5 2.5 (diethylamino)propylamine(DMAPA)/neodecanoic acid 15 Zn(1-methylimidazole)₂(2- 2.0 3.0 7.5ethylhexanoate)₂ + 1- dimethylamino-2-propanol (DMPA)/2-ethylhexanoicacid 16 Zn(tetramethylguanidine)2 2.0 2.5 4.0 (neodecanoate)₂ +1-dimethylamino- 2-propanol (DMPA)/neodecanoic acid 17Zn(DBU)₂(neodecanoate)₂ + 1- 2.0 2.5 4.5 dimethylamino-2-propanol(DMPA)/neodecanoic acid 18 Zn(1-methylimidazole)₂(2- 2.0 3.0 8.0ethylhexanoate)₂ + 2- (dimethylamino)ethanol (DMEA)/2- ethylhexanoicacid 19 Zn(tetramethylguanidine)₂ 2.0 2.5 4.0 (neodecanoate)₂+2-(dimethylamino) ethanol (DMEA)/neodecanoic acid 20Zn(DBU)₂(neodecanoate)₂ + 2- 2.0 2.5 4.5 (dimethylamino)ethanol(DMEA)/neodecanoic acid

Examples 11-20 in TABLE 8 demonstrate that the mixtures of zinc amidinecomplexes (50% by weight) and amine/carboxylic acid salts (50% byweight) are effective catalysts for a trimethoxysilane terminatedpolyester (TMS) based sealant.

Cure Studies in a Diethoxysilane Terminated Polyether Urea System

Sealant Preparation: Dispense 30 grams of the uncatalyzed sealant (DES)described in TABLE 9 from cartridge tube into speed mixer containerusing a caulk gun. Add catalyst and mix on the speed mixer using Program3 (30 seconds @ 1500 rpm then 2 minutes @ 2200 rpm). Use adjustabledoctor blade to apply 3 mm of the blend onto a paper substrate. Monitorcure time by applying a folded 1″×2″ strip of paper onto the castingsurface and measuring tack after applying weights onto the folded paperstrips. Gauge the degree of cure based on the time needed for thecasting to be tack free after application of 20, 50, 100, 200, and 500gram weights. Allow the weights to remain on the paper for approximately5 seconds before lifting the paper strip. Touch dry time was determinedby passing the weight of 20 grams and through dry time was determined bypassing the weight of 500 grams. The formulation is tabulated in TABLE9. The catalyst levels of dioctyltin diacac (Control) and disclosurecatalysts were 0.6% and 2.0% based on total formulation, respectively.

TABLE 9 Ingredient % by weight Eastman 168 23.4 HiPflex 100 27.7 UltraPflex 22.2 KRT 12-C TiO2 3.3 Ethanox 310 0.3 Tinuvin 770 0.3 p-TSI 0.8Diethoxysilane (DES) 20.5 Aerosil R202 1.4 Dioctyltin Diacac (Control)0.6 Disclosure Catalyst 2.0

TABLE 10 % Touch Through Exam- Cata- Dry Dry ples Catalysts lyst HoursHours 21 Dioctyltin Diacac (Control) 0.6 120+ 120+ 22Zn(1-methylimidazole)₂(2- 2.0  8 24 ethylhexanoate)₂ + 3-(diethylamino)propylamine (DMAPA)/2-ethylhexanoic acid 23Zn(tetramethylguanidine)₂ 2.0  3  8 (neodecanoate)₂ + 3-(diethylamino)propylamine (DMAPA)/neodecanoic acid 24Zn(DBU)₂(neodecanoate)2 + 3- 2.0  3  8 (diethylamino)propylamine(DMAPA)/neodecanoic acid 25 Zn(1-methylimidazole)₂(2- 2.0  8 32ethylhexanoate)₂ + 1- dimethylamino-2-propanol (DMPA)/2-ethylhexanoicacid 26 Zn(tetramethylguanidine)₂ 2.0  6 16 (neodecanoate)₂ +1-dimethylamino- 2-propanol (DMPA)/neodecanoic acid 27Zn(DBU)₂(neodecanoate)₂ + 1- 2.0  5 16 dimethylamino-2-propanol(DMPA)/neodecanoic acid 28 Zn(1-methylimidazole)₂(2- 2.0  8 32ethylhexanoate)₂ + 2- (dimethylamino)ethanol (DMEA)/2- ethylhexanoicacid 29 Zn(tetramethylguanidine)₂ 2.0  7 16 (neodecanoate)₂ +2-(dimethylamino) ethanol (DMEA)/neodecanoic acid 30Zn(DBU)2(neodecanoate)₂ + 2- 2.0  6 16 (dimethylamino)ethanol(DMEA)/neodecanoic acid

Examples 21-30 in TABLE 10 demonstrate that the mixtures of zinc amidinecomplexes (50% by weight) and amine/carboxylic acid salts (50% byweight) are effective catalysts for a diethoxysilane terminatedpolyether urea (DES) based sealant.

What is claimed is:
 1. A silanol condensation catalyst consisting of amixture of one or more metal amidine complexes and one or more aminecarboxylate salts, wherein the amidine is a guanidine, and wherein theguanidine is 1-phenylguanidine and/or 1-(o-tolyl)guanidine.
 2. Thesilanol condensation catalyst of claim 1, wherein the one or more metalamidine complexes is of the chemical formulaM(amidine)_(w)(carboxylate)₂, wherein w is an integer from 1 to
 4. 3.The silanol condensation catalyst of claim 1, wherein the metal of theone or more metal amidine complexes is zinc, lithium, sodium, magnesium,barium, potassium, calcium, bismuth, cadmium, aluminum, zirconium,hafnium, titanium, lanthanum, vanadium, niobium, tantalum, tellurium,molybdenum, tungsten, or cesium.
 4. The silanol condensation catalyst ofclaim 3, wherein the metal of the metal amidine complex is zinc orbismuth.
 5. The silanol condensation catalyst of claim 1, wherein theone or more amine carboxylate salts is derived from a carboxylate of thefollowing formula:

wherein R₁₁ is hydrogen, C₁-C₂₅ alkyl, C₂-C₂₅ alkyl interrupted byoxygen or sulfur; C₂-C24 alkenyl, C₄-C₁₅ cycloalkyl which isunsubstituted or substituted by C₁-C₄ allyl and/or carboxyl; C₅-C₁₅cycloalkenyl which is unsubstituted or substituted by C₁-C₄ alkyl and/orcarboxyl; C₁₃-C₂₆ polycycloalkyl, C₇-C₉ phenylalkyl which isunsubstituted or substituted on the phenyl ring by C₁-C₄ alkyl; —COR₁₆,a 5- or 6-membered heterocyclic ring which is unsubstituted orsubstituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen or carboxyl; a 5- or6-membered heterocyclic ring which is benzo-fused and is unsubstitutedor substituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen or carboxyl; or aradical of one of the following formulae:

wherein R₁₂, R₁₃, R₁₄ and R₁₅ independently are hydrogen, hydroxyl,C₁-C₁₈ alkoxy, C₂-C₁₈ alkoxy which is interrupted by oxygen or sulfur;C₁-C₂₅ alkyl, C₂-C₂₅ alkyl which is interrupted by oxygen or sulfur;C₂-C₂₄ alkenyl, C₅-C₁₅ cycloalkyl which is unsubstituted or substitutedby C₁-C₄ alkyl; C₅-C₁₅ cycloalkenyl which is unsubstituted orsubstituted by C₁-C₄ alkyl; phenyl or naphthyl which is unsubstituted orsubstituted by C₁-C₄ alkyl; C₇-C₉ phenylalkyl which is unsubstituted orsubstituted on the phenyl ring by C₁-C₄ alkyl; C₁₀-C₁₂ naphthylalkylwhich is unsubstituted or substituted on the naphthyl ring system byC₁-C₄ alkyl; or are —COR₆, with the proviso that, if one of the radicalsR₁₂, R₁₃, R₁₄ and R₁₅ is hydroxyl, the other radical attached to thesame carbon atom is other than hydroxyl; or else R₁₂ and R₁₃ or R₁₄ andR₁₅, together with the carbon atom to which they are attached, form anunsubstituted or C₁-C₄ alkyl-substituted C₅-C₁₂ cycloalkylidene ring;wherein R₁₆ is hydroxyl, C₁-C₁₈ alkoxy, C₂-C₁₈ alkoxy which isinterrupted by oxygen or sulfur; or

wherein R₃₇, R₃₈, R₃₉, R₄₀ and R₄₁ are independently hydrogen, hydroxyl,halogen, nitro, cyano, CF₃, —COR₆, C₁-C₂₅ alkyl, C₂-C₂₅ alkyl which isinterrupted by oxygen or sulfur; C₁-C₂₅ haloalkyl, C₁-C₁₈ alkoxy, C₂-C₁₈alkoxy which is interrupted by oxygen or sulfur; C₁-C₁₈ alkylthio,C₂-C₂₄ alkenyl, C₅-C₁₅ cycloalkyl which is unsubstituted or substitutedby C₁-C₄ alkyl; C₅-C₁₅ cycloalkenyl which is unsubstituted orsubstituted by C₁-C₄ alkyl; phenyl or naphthyl which is unsubstituted orsubstituted by C₁-C₄ alkyl; C₇-C₉ phenylalkyl which is unsubstituted orsubstituted on the phenyl ring by C₁-C₄ alkyl; C₁₀-C₁₂ naphthylalkylwhich is unsubstituted or substituted on the naphthyl ring system byC₁-C₄ alkyl; phenoxy or naphthoxy which is unsubstituted or substitutedby C₁-C₄ alkyl; C₇-C₉ phenylalkoxy which is unsubstituted or substitutedon the phenyl ring by C₁-C₄ alkyl; C₁₀-C₁₂ naphthylalkoxy which isunsubstituted or substituted on the naphthyl ring system by C₁-C₄ alkyl;or else the radicals R₃₈ and R₃₉ or the radicals R₃₉ and R₄₀ or theradicals R₄₀ and R₄₁ or the radicals R₃₇ and R₄₁, together with thecarbon atoms to which they are attached, form an unsubstituted or C₁-C₄alkyl-, halogen- or C₁-C₄ alkoxy-substituted benzo ring, with theproviso that at least one of the radicals R₃₇, R₃₈, R₃₉, R₄₀ and R₄₁ ishydrogen; R₄₂ is hydroxyl, halogen, nitro, cyano, CF₃, C₁-C₂₅ alkyl,C₂-C₂₅ alkyl which is interrupted by oxygen or sulfur; C₁-C₂₅ haloalkyl,alkoxy, C₂-C₁₈ alkoxy which is interrupted by oxygen or sulfur; C₁-C₁₈alkylthio or C₂-C₂₄ alkenyl; R₄₃ and R₄₄ are independently hydrogen,C₁-C₂₅ alkyl, C₁-C₁₈ alkoxy or —Y—(CH₂)_(s)COR₆; R₄₅ and R₄₆ areindependently hydrogen, C₁-C₂₅ alkyl, C₃-C₂₅ alkyl which is interruptedby oxygen or sulfur; C₂-C₂₄ alkenyl, C₅-C₁₅ cycloalkyl which isunsubstituted or substituted by C₁-C₄ alkyl; phenyl or naphthyl which isunsubstituted or substituted by C₁-C₄ alkyl; X₁₁ is a direct bond,oxygen, sulfur, C(O), C₁-C₁₈ alkylene, C₂-C₁₈ alkylene which isinterrupted by oxygen or sulfur; C₂-C₁₈ alkenylene, C₂-C₁₈ alkynylene,C₂-C₂₀ alkylidene, C₇-C₂₀ phenylalkylidene or C₅-C₈ cycloalkylene, withthe proviso that, if m and n are 0, X₁₁ is other than oxygen and sulfur;Y is oxygen or

R_(a) is hydrogen or C₁-C₈ alkyl; e and f independently of one anotherare integers from 0 to 10; p is an integer from 0 to 4; and s is aninteger from 1 to
 8. 6. The silanol condensation catalyst of claim 1,wherein the one or more amine carboxylate salts is derived from an amineof general formulaR⁵¹ _(d)YR⁵²NHR⁵³ wherein Y is O, N, S or P wherein when Y is O or S, dis 1 and when Y is N or P, d is 2; each R⁵¹ is a hydrogen atom, or asubstituted or unsubstituted hydrocarbon group having 1 to 20 carbonatoms; when d is two, R⁵¹ may be the same or different; R⁵² is asubstituted or unsubstituted bivalent hydrocarbon group having 1 to 10carbon atoms; and R⁵³ is a hydrogen atom or a methyl group.
 7. A silanolcondensation catalyst consisting of a mixture of one or more metalamidine complexes and one or more amine carboxylate salts, wherein theone or more amine carboxylate salts is derived from a phenyl guanidinerepresented by formulae

wherein the each R² independently is hydrogen, halogen, hydroxyl, anamino group, a nitro group, a cyano group, a sulfonic acid group, or anorganic group; and a is an integer of 0 to
 5. 8. The silanolcondensation catalyst of claim 1, wherein the one or more metal amidinecomplexes is of the chemical formula metal (amidine)₂(carboxylate)x,wherein x is the oxidation state of the metal.
 9. The silanolcondensation catalyst of claim 1, wherein the one or more aminecarboxylate salts is derived from amine of general formulaR⁵¹ _(d)YR⁵²NHR⁵³ wherein Y is O, N, S or P wherein when Y is O or S, dis 1 and when Y is N or P, d is 2; each R⁵¹ is a hydrogen atom, or asubstituted or unsubstituted hydrocarbon group having 1 to 20 carbonatoms; when d is two, R⁵¹ may be the same or different; R⁵² is asubstituted or unsubstituted bivalent hydrocarbon group having 1 to 10carbon atoms; and R⁵³ is a hydrogen atom or a methyl group.
 10. Asilanol condensation catalyst consisting of a mixture of one or moremetal amidine complexes and one or more amine carboxylate salts, whereinthe one or more amine carboxylate salts is derived from an amineselected from monoethanolamine, 3-hydroxypropylamine,2-(2-aminoethylamino)ethanol, 1-dimethylamino-2-propanol,diethylamino-2-propanol, 2-(dimethylamino)ethanol,2-(diethylamino)ethanol, 2-dimethylamino-2-methyl-1-propanol,ethylenediamine, N-methylethylenediamine, 1, 3-propanediamine,N-methyl-1, 3-propanediamine, N, N′-dimethyl-1, 3-propanediamine,3-(diethylamino)propyl amine, 3-(dimethylamino)propyl amine anddiethylenetriamine.
 11. The silanol condensation catalyst of claim 1,wherein the one or more amine carboxylate salts is derived from acarboxylic acid selected from hexanoic acid, heptanoic acid2-ethylhexanoic acid, octanoic acid, oleic acid, lauric acid, naphthenicacid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid,neodecanoic acid, and versatic acid.
 12. A silanol condensation catalystconsisting of a mixture of one or more metal amidine complexes and oneor more amine carboxylate salts, wherein the one or more aminecarboxylate salts is derived from a carboxylic acid in which theα-carbon atom of the carboxyl group is a quaternary carbon atom.
 13. Thesilanol condensation catalyst of claim 7, wherein the one or more metalamidine complexes is of the chemical formulaM(amidine)_(w)(carboxylate)₂, wherein w is an integer from 1 to
 4. 14.The silanol condensation catalyst of claim 7, wherein the metal of theone or more metal amidine complexes is zinc, lithium, sodium, magnesium,barium, potassium, calcium, bismuth, cadmium, aluminum, zirconium,hafnium, titanium, lanthanum, vanadium, niobium, tantalum, tellurium,molybdenum, tungsten, or cesium.
 15. The silanol condensation catalystof claim 14, wherein the metal of the metal amidine complex is zinc orbismuth.
 16. The silanol condensation catalyst of claim 7, wherein theone or more metal amidine complexes is derived from an amidine offormulae I-VIII

wherein R¹ is hydrogen, C₁-C₃₆ alkyl, C₂-C₂₅ alkyl interrupted by oxygenor sulfur, C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which is unsubstituted orsubstituted by C₁-C₄ allyl and/or carboxyl, C₅-C₁₅ cycloalkenyl which isunsubstituted or substituted by C₁-C₄ alkyl and/or carboxyl, C₁₃-C₂₆polycycloalkyl, C₇-C₉ phenylalkyl which is unsubstituted or substitutedon the phenyl ring by C₁-C₄ alkyl, an amine group which is optionallysubstituted, or a hydroxyl group which is optionally etherified with ahydrocarbyl group having up to 8 carbon atoms; R² and R³ are eachindependently hydrogen or C₁-C₂₅ alkyl, C₂-C₂₅ alkyl interrupted byoxygen or sulfur, C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which isunsubstituted or substituted by C₁-C₄ allyl and/or carboxyl, C₅-C₁₅cycloalkenyl which is unsubstituted or substituted by C₁-C₄ alkyl and/orcarboxyl, C₁₃-C₂₆ polycycloalkyl, C₇-C₉ phenylalkyl which isunsubstituted or substituted on the phenyl ring by C₁-C₄ alkyl, or R²and R³ are joined to one another by an N═C—N linkage to form aheterocyclic ring or a fused bicyclic ring with one or more heteroatoms;R⁴ is hydrogen, or C₁-C₃₆ alkyl, C₁-C₃₆ alkyl interrupted by oxygen orsulfur, C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which is unsubstituted orsubstituted by C₁-C₄ allyl and/or carboxyl, C₅-C₁₅ cycloalkenyl which isunsubstituted or substituted by C₁-C₄ alkyl and/or carboxyl, C₁₃-C₂₆polycycloalkyl, C₇-C₉ phenylalkyl which is unsubstituted or substitutedon the phenyl ring by C₁-C₄ alkyl) or a hydroxyl group which can beoptionally etherified with a hydrocarbyl group having up to 8 carbonatoms; R⁵, R⁶, R⁷, and R⁸ are independently hydrogen, alkyl, substitutedalkyl, hydroxyalkyl, aryl, aralkyl, cycloalkyl, heterocyclics, ether,thioether, halogen, —N(R)₂, polyethylene polyamines, nitro groups, ketogroups, ester groups, or carbonamide groups optionally substituted withalkyl, substituted alkyl, aryl, aralkyl, cycloalkyl, heterocycles,ether, thioether, halogen, —N(R)₂, polyethylene polyamines, nitrogroups, keto groups or ester groups; R⁹, R¹⁰ and R¹¹ are independentlyhydrogen, alkyl, alkenyl or alkoxy of 1 to 36 carbons, cycloalkyl of 6to 32 carbons, alkylamino of 1 to 36 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenyl, hydroxyalkyl, hydroxycycloalkyl of 1 to 20 carbonatoms, methoxyalkyl of 1 to 20 carbon atoms, aralkyl of 7 to 9 carbonatoms wherein the aryl group of the aralkyl is optionally furthersubstituted by alkyl of 1 to 36 carbon atoms, ether, thioether, halogen,—N(R″)₂, polyethylene polyamines, nitro groups, keto groups, estergroups, or carbonamide groups, and wherein the alkyl group of thearalkyl is optionally substituted with alkyl, substituted alkyl, aryl,aralkyl, cycloalkyl, heterocyclics, ether, thioether, halogen, —N(R″)₂,polyethylene polyamines, nitro groups, keto groups or ester groups,wherein R″ of —N(R″)₂ is alkyl, alkylene, aryl, aralkyl, cycloalkyl orheterocyclic radical, optionally substituted with halogen, nitro, alkyl,alkoxy or amino; m=1 or 2; wherein when m=1, R is hydrogen or aplurality of radicals optionally joined by hetero atoms O, N or S; n=2or 3; R₂₁-R₂₉ are independently hydrogen, alkyl, cycloalkyl, aryl,aromatic, organometallic, a polymeric structure or together can form acycloalkyl, aryl, or an aromatic structure; a is 1, 2, or 3; and b is 1,2, or
 3. 17. The silanol condensation catalyst of claim 16, wherein theamidine of the metal amidine complex is an amidine of formula II or IV.18. The silanol condensation catalyst of claim 17, wherein the amidineis 1,1,3,3-tetramethyl guanidine or 1-methylimidazole.
 19. The silanolcondensation catalyst of claim 7, wherein the amidine is a guanidine,wherein the guanidine is 1-phenylguanidine and/or 1-(o-tolyl)guanidine.20. The silanol condensation catalyst of claim 7, wherein the amidine isat least one member selected from the group consisting of1,2-dimethyl-1,4,5,6-tetrahydropyrimidine,1-ethyl-2-methyl-1,4,5,6-tetrahydropyrimidine,1,2-diethyl-1,4,5,6-tetrahydropyrimidine,1-n-propyl-2-methyl-1,4,5,6-tetrahydropyrimidine,1-isopropyl-2-methyl-1,4,5,6-tetrahydropyrimidine,1-ethyl-2-n-propyl-1,4,5,6-tetrahydropyrimidine and1-ethyl-2-isopropyl-1,4,5,6-tetrahydropyrimidine.
 21. The silanolcondensation catalyst of claim 7, wherein the amidine is at least oneguanidine selected from the group consisting of7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-ethyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-n-propyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-isopropyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-n-butyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-isobutyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-tert-butyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-cyclohexyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-n-octyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-2-ethylhexyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene and7-decyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene.
 22. The silanolcondensation catalyst of claim 17, wherein the carboxylate of the metalamidine complex is heptanoate, hexanoate, laurate, oleate, versatate,octoate, neodecanoate, naphthenate, stearate, or oxalate.
 23. Thesilanol condensation catalyst of claim 7, wherein the one or more metalamidine complexes is of the chemical formula metal(amidine)₂(carboxylate)x, wherein x is the oxidation state of the metal.24. The silanol condensation catalyst of claim 10, wherein the one ormore metal amidine complexes is of the chemical formulaM(amidine)_(w)(carboxylate)₂, wherein w is an integer from 1 to
 4. 25.The silanol condensation catalyst of claim 10, wherein the metal of theone or more metal amidine complexes is zinc, lithium, sodium, magnesium,barium, potassium, calcium, bismuth, cadmium, aluminum, zirconium,hafnium, titanium, lanthanum, vanadium, niobium, tantalum, tellurium,molybdenum, tungsten, or cesium.
 26. The silanol condensation catalystof claim 25, wherein the metal of the metal amidine complex is zinc orbismuth.
 27. The silanol condensation catalyst of claim 10, wherein theone or more metal amidine complexes is derived from an amidine offormulae I-VIII

wherein R¹ is hydrogen, C₁-C₃₆ alkyl, C₂-C₂₅ alkyl interrupted by oxygenor sulfur, C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which is unsubstituted orsubstituted by C₁-C₄ allyl and/or carboxyl, C₅-C₁₅ cycloalkenyl which isunsubstituted or substituted by C₁-C₄ alkyl and/or carboxyl, C₁₃-C₂₆polycycloalkyl, C₇-C₉ phenylalkyl which is unsubstituted or substitutedon the phenyl ring by C₁-C₄ alkyl, an amine group which is optionallysubstituted, or a hydroxyl group which is optionally etherified with ahydrocarbyl group having up to 8 carbon atoms; R² and R³ are eachindependently hydrogen or C₁-C₂₅ alkyl, C₂-C₂₅ alkyl interrupted byoxygen or sulfur, C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which isunsubstituted or substituted by C₁-C₄ allyl and/or carboxyl, C₅-C₁₅cycloalkenyl which is unsubstituted or substituted by C₁-C₄ alkyl and/orcarboxyl, C₁₃-C₂₆ polycycloalkyl, C₇-C₉ phenylalkyl which isunsubstituted or substituted on the phenyl ring by C₁-C₄ alkyl, or R²and R³ are joined to one another by an N═C—N linkage to form aheterocyclic ring or a fused bicyclic ring with one or more heteroatoms;R⁴ is hydrogen, or C₁-C₃₆ alkyl, C₁-C₃₆ alkyl interrupted by oxygen orsulfur, C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which is unsubstituted orsubstituted by C₁-C₄ allyl and/or carboxyl, C₅-C₁₅ cycloalkenyl which isunsubstituted or substituted by C₁-C₄ alkyl and/or carboxyl, C₁₃-C₂₆polycycloalkyl, C₇-C₉ phenylalkyl which is unsubstituted or substitutedon the phenyl ring by C₁-C₄ alkyl) or a hydroxyl group which can beoptionally etherified with a hydrocarbyl group having up to 8 carbonatoms; R⁵, R⁶, R⁷, and R⁸ are independently hydrogen, alkyl, substitutedalkyl, hydroxyalkyl, aryl, aralkyl, cycloalkyl, heterocyclics, ether,thioether, halogen, —N(R)₂, polyethylene polyamines, nitro groups, ketogroups, ester groups, or carbonamide groups optionally substituted withalkyl, substituted alkyl, aryl, aralkyl, cycloalkyl, heterocycles,ether, thioether, halogen, —N(R)₂, polyethylene polyamines, nitrogroups, keto groups or ester groups; R⁹, R¹⁰ and R¹¹ are independentlyhydrogen, alkyl, alkenyl or alkoxy of 1 to 36 carbons, cycloalkyl of 6to 32 carbons, alkylamino of 1 to 36 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenyl, hydroxyalkyl, hydroxycycloalkyl of 1 to 20 carbonatoms, methoxyalkyl of 1 to 20 carbon atoms, aralkyl of 7 to 9 carbonatoms wherein the aryl group of the aralkyl is optionally furthersubstituted by alkyl of 1 to 36 carbon atoms, ether, thioether, halogen,—N(R″)₂, polyethylene polyamines, nitro groups, keto groups, estergroups, or carbonamide groups, and wherein the alkyl group of thearalkyl is optionally substituted with alkyl, substituted alkyl, aryl,aralkyl, cycloalkyl, heterocyclics, ether, thioether, halogen, —N(R″)₂,polyethylene polyamines, nitro groups, keto groups or ester groups,wherein R″ of —N(R″)₂ is alkyl, alkylene, aryl, aralkyl, cycloalkyl orheterocyclic radical, optionally substituted with halogen, nitro, alkyl,alkoxy or amino; m=1 or 2; wherein when m=1, R is hydrogen or aplurality of radicals optionally joined by hetero atoms O, N or S; n=2or 3; R₂₁-R₂₉ are independently hydrogen, alkyl, cycloalkyl, aryl,aromatic, organometallic, a polymeric structure or together can form acycloalkyl, aryl, or an aromatic structure; a is 1, 2, or 3; and b is 1,2, or
 3. 28. The silanol condensation catalyst of claim 27, wherein theamidine of the metal amidine complex is an amidine of formula II or IV.29. The silanol condensation catalyst of claim 10, wherein the amidineis 1,1,3,3-tetramethyl guanidine or 1-methylimidazole.
 30. The silanolcondensation catalyst of claim 10, wherein the guanidine is1-phenylguanidine and/or 1-(o-tolyl)guanidine.
 31. The silanolcondensation catalyst of claim 10, wherein the amidine is at least onemember selected from the group consisting of1,2-dimethyl-1,4,5,6-tetrahydropyrimidine,1-ethyl-2-methyl-1,4,5,6-tetrahydropyrimidine,1,2-diethyl-1,4,5,6-tetrahydropyrimidine,1-n-propyl-2-methyl-1,4,5,6-tetrahydropyrimidine,1-isopropyl-2-methyl-1,4,5,6-tetrahydropyrimidine,1-ethyl-2-n-propyl-1,4,5,6-tetrahydropyrimidine and1-ethyl-2-isopropyl-1,4,5,6-tetrahydropyrimidine.
 32. The silanolcondensation catalyst of claim 10, wherein the amidine is at least oneguanidine selected from the group consisting of7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-ethyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-n-propyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-isopropyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-n-butyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-isobutyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-tert-butyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-cyclohexyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-n-octyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-2-ethylhexyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene and7-decyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene.
 33. The silanolcondensation catalyst of claim 10, wherein the carboxylate of the metalamidine complex is heptanoate, hexanoate, laurate, oleate, versatate,octoate, neodecanoate, naphthenate, stearate, or oxalate.
 34. Thesilanol condensation catalyst of claim 10, wherein the one or more metalamidine complexes is of the chemical formula metal(amidine)₂(carboxylate)x, wherein x is the oxidation state of the metal.35. The silanol condensation catalyst of claim 12, wherein the one ormore metal amidine complexes is of the chemical formulaM(amidine)_(w)(carboxylate)₂, wherein w is an integer from 1 to
 4. 36.The silanol condensation catalyst of claim 12, wherein the metal of theone or more metal amidine complexes is zinc, lithium, sodium, magnesium,barium, potassium, calcium, bismuth, cadmium, aluminum, zirconium,hafnium, titanium, lanthanum, vanadium, niobium, tantalum, tellurium,molybdenum, tungsten, or cesium.
 37. The silanol condensation catalystof claim 36, wherein the metal of the metal amidine complex is zinc orbismuth.
 38. The silanol condensation catalyst of claim 12, wherein theone or more metal amidine complexes is derived from an amidine offormulae I-VIII

wherein R¹ is hydrogen, C₁-C₃₆ alkyl, C₂-C₂₅ alkyl interrupted by oxygenor sulfur, C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which is unsubstituted orsubstituted by C₁-C₄ allyl and/or carboxyl, C₅-C₁₅ cycloalkenyl which isunsubstituted or substituted by C₁-C₄ alkyl and/or carboxyl, C₁₃-C₂₆polycycloalkyl, C₇-C₉ phenylalkyl which is unsubstituted or substitutedon the phenyl ring by C₁-C₄ alkyl, an amine group which is optionallysubstituted, or a hydroxyl group which is optionally etherified with ahydrocarbyl group having up to 8 carbon atoms; R² and R³ are eachindependently hydrogen or C₁-C₂₅ alkyl, C₂-C₂₅ alkyl interrupted byoxygen or sulfur, C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which isunsubstituted or substituted by C₁-C₄ allyl and/or carboxyl, C₅-C₁₅cycloalkenyl which is unsubstituted or substituted by C₁-C₄ alkyl and/orcarboxyl, C₁₃-C₂₆ polycycloalkyl, C₇-C₉ phenylalkyl which isunsubstituted or substituted on the phenyl ring by C₁-C₄ alkyl, or R²and R³ are joined to one another by an N═C—N linkage to form aheterocyclic ring or a fused bicyclic ring with one or more heteroatoms;R⁴ is hydrogen, or C₁-C₃₆ alkyl, C₁-C₃₆ alkyl interrupted by oxygen orsulfur, C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkyl which is unsubstituted orsubstituted by C₁-C₄ allyl and/or carboxyl, C₅-C₁₅ cycloalkenyl which isunsubstituted or substituted by C₁-C₄ alkyl and/or carboxyl, C₁₃-C₂₆polycycloalkyl, C₇-C₉ phenylalkyl which is unsubstituted or substitutedon the phenyl ring by C₁-C₄ alkyl) or a hydroxyl group which can beoptionally etherified with a hydrocarbyl group having up to 8 carbonatoms; R⁵, R⁶, R⁷, and R⁸ are independently hydrogen, alkyl, substitutedalkyl, hydroxyalkyl, aryl, aralkyl, cycloalkyl, heterocyclics, ether,thioether, halogen, —N(R)₂, polyethylene polyamines, nitro groups, ketogroups, ester groups, or carbonamide groups optionally substituted withalkyl, substituted alkyl, aryl, aralkyl, cycloalkyl, heterocycles,ether, thioether, halogen, —N(R)₂, polyethylene polyamines, nitrogroups, keto groups or ester groups; R⁹, R¹⁰ and R¹¹ are independentlyhydrogen, alkyl, alkenyl or alkoxy of 1 to 36 carbons, cycloalkyl of 6to 32 carbons, alkylamino of 1 to 36 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenyl, hydroxyalkyl, hydroxycycloalkyl of 1 to 20 carbonatoms, methoxyalkyl of 1 to 20 carbon atoms, aralkyl of 7 to 9 carbonatoms wherein the aryl group of the aralkyl is optionally furthersubstituted by alkyl of 1 to 36 carbon atoms, ether, thioether, halogen,—N(R″)₂, polyethylene polyamines, nitro groups, keto groups, estergroups, or carbonamide groups, and wherein the alkyl group of thearalkyl is optionally substituted with alkyl, substituted alkyl, aryl,aralkyl, cycloalkyl, heterocyclics, ether, thioether, halogen, —N(R″)₂,polyethylene polyamines, nitro groups, keto groups or ester groups,wherein R″ of —N(R″)₂ is alkyl, alkylene, aryl, aralkyl, cycloalkyl orheterocyclic radical, optionally substituted with halogen, nitro, alkyl,alkoxy or amino; m=1 or 2; wherein when m=1, R is hydrogen or aplurality of radicals optionally joined by hetero atoms 0, N or S; n=2or 3; R₂₁-R₂₉ are independently hydrogen, alkyl, cycloalkyl, aryl,aromatic, organometallic, a polymeric structure or together can form acycloalkyl, aryl, or an aromatic structure; a is 1, 2, or 3; and b is 1,2, or
 3. 39. The silanol condensation catalyst of claim 38, wherein theamidine of the metal amidine complex is an amidine of formula II or IV.40. The silanol condensation catalyst of claim 12, wherein the amidineis 1,1,3,3-tetramethyl guanidine or 1-methylimidazole.
 41. The silanolcondensation catalyst of claim 12, wherein the guanidine is1-phenylguanidine and/or 1-(o-tolyl)guanidine.
 42. The silanolcondensation catalyst of claim 12, wherein the amidine is at least onemember selected from the group consisting of1,2-dimethyl-1,4,5,6-tetrahydropyrimidine,1-ethyl-2-methyl-1,4,5,6-tetrahydropyrimidine,1,2-diethyl-1,4,5,6-tetrahydropyrimidine,1-n-propyl-2-methyl-1,4,5,6-tetrahydropyrimidine,1-isopropyl-2-methyl-1,4,5,6-tetrahydropyrimidine,1-ethyl-2-n-propyl-1,4,5,6-tetrahydropyrimidine and1-ethyl-2-isopropyl-1,4,5,6-tetrahydropyrimidine.
 43. The silanolcondensation catalyst of claim 12, wherein the amidine is at least oneguanidine selected from the group consisting of7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-ethyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-n-propyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-isopropyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-n-butyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-isobutyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-tert-butyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-cyclohexyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-n-octyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene,7-2-ethylhexyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene and7-decyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene.
 44. The silanolcondensation catalyst of claim 12, wherein the carboxylate of the metalamidine complex is heptanoate, hexanoate, laurate, oleate, versatate,octoate, neodecanoate, naphthenate, stearate, or oxalate.
 45. Thesilanol condensation catalyst of claim 12, wherein the one or more metalamidine complexes is of the chemical formula metal(amidine)₂(carboxylate)x, wherein x is the oxidation state of the metal.46. The silanol condensation catalyst of claim 12, wherein the one ormore amine carboxylate salts is derived from a carboxylic acid selectedfrom hexanoic acid, heptanoic acid 2-ethylhexanoic acid, octanoic acid,oleic acid, lauric acid, naphthenic acid, 2,2-dimethyloctanoic acid,2-ethyl-2,5-dimethylhexanoic acid, neodecanoic acid, and versatic acid.